CN109928381B - Macroporous carbon and preparation method thereof - Google Patents
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Abstract
The invention provides macroporous carbon and a preparation method thereof. The preparation method comprises the steps of firstly screening a Beta molecular sieve; then putting the Beta molecular sieve into a sodium benzoate solution for treatment; then mixing Beta molecular sieve, saccharides and water, and stirring and carrying out ultrasonic treatment; then drying treatment is carried out; then high-temperature treatment is carried out; and finally, treating in an alkali solution to obtain the macroporous carbon material. The method does not use expensive organic additives, and the prepared macroporous carbon material has uniform pore size distribution.
Description
Technical Field
The invention belongs to the field of synthesis of porous inorganic materials, and particularly relates to a method for synthesizing macroporous carbon.
Background
According to the classification of the international union of pure and applied chemistry, porous materials can be divided into three main categories: macroporous materials (directly more than 50 nm), mesoporous materials (not more than 2nm and not more than 50 nm) and microporous materials (directly less than 2 nm). Microporous materials and mesoporous materials have been the focus of research and application because of their successful application in the fields of industrial catalysis and separation. In recent years, with the fact that the defect that the conventional small pore molecular sieve and mesoporous material are difficult to allow macromolecules to enter the interior of a pore channel and the advantages of other physical and chemical characteristics are made up by macroporous materials in the fields of macromolecule catalysis, separation and the like, the macroporous materials gradually attract the attention of researchers and become the popular field of research.
By means of SiO2The preparation method of the three-dimensional ordered macroporous carbon with high specific surface area (Nanjing university of aerospace, 2005, 37 (5): 593-: (1) Firstly, the Stobber method is adopted to synthesize the monodisperse SiO2Centrifuging and washing the colloidal microspheres, dispersing the colloidal microspheres by using ethanol, standing the colloidal microspheres for 10 to 30 days at normal temperature and normal pressure, and reacting the SiO2The microspheres self-assemble into ordered opal structures under the action of gravity and are then dried at 120 ℃ for 12 h. (2) Then filling the gaps of the template with sucrose, and repeating the carbonization process to prepare the macroporous carbon materialAnd (5) feeding.
"double template method synthesis mesopore/macropore secondary pore carbon material" (physical chemistry report, 2007, 23(5):
757 and 760) preparing a mesoporous/macroporous secondary pore carbon material by a colloidal crystal template method, which comprises the following steps: firstly, preparing nearly monodisperse silicon dioxide spheres according to a Stober method, and self-assembling under the action of gravity to form a template; dissolving the prepared phenolic resin oligomer, mixing the phenolic resin oligomer with organic matters such as ethanol, Pluronic F127 and the like, then soaking the mixture into a silicon dioxide template, and standing the mixture at room temperature until the solution is dried; and then completely polymerizing the phenolic resin, carbonizing the phenolic resin under the nitrogen protection atmosphere, and removing silicon dioxide by hydrofluoric acid to obtain the mesoporous/macroporous secondary pore carbon material, wherein the diameter of a macropore of the carbon material is about 230nm, and the diameter of a mesopore is about 10 nm.
CN102295281A, a method for preparing hierarchical porous carbon by taking hollow mesoporous silicon spheres as templates, wherein a phenolic resin ethanol solution is impregnated into mesoporous channels of the hollow mesoporous silicon spheres, and then the phenolic resin is primarily cured, deeply cured, carbonized and removed from the templates, so that the hierarchical porous carbon with macropores, mesopores and micropores is finally prepared. The template is a hollow mesoporous silicon sphere, the hollow mesoporous silicon sphere is provided with a hollow core and a mesoporous wall, the aperture of the hollow core is 300-800nm, and the mesoporous wall is about 25-60 nm. The aperture of the prepared hierarchical porous carbon is 300-800nm, and the wall thickness is 25-60 nm.
CN103482597A, a method for preparing medium and large pore carbon, mixing resin and curing agent, heating and curing; and crushing the curing material, mixing the crushed curing material with a pore-forming agent and a propping agent, fully mixing the materials, pressing the mixture into a prefabricated body, and carbonizing the prefabricated body at high temperature to prepare the medium-large pore carbon, wherein the pore diameter of a large pore of the medium-large pore carbon is 50nm to 10 mu m. The pore-forming agent is polyvinyl alcohol, polyvinyl butyral and polyththalimide resin, and has the function of manufacturing macropores, and the aperture can be adjusted by changing the proportion of the carbon-containing material and the pore-forming agent as well as the temperature, the pressing pressure and the material proportion; the propping agent is graphite powder, activated carbon fiber, carbon nano-tube or graphite fiber, and has the function of preventing the matrix from shrinking in the carbonization process to a certain extent, so that the pore structure of the porous carbon tends to be stable and the pore diameter is enlarged.
In the synthetic method, compared with other types of hard templates, the size of the template of the Beta molecular sieve can be accurately adjusted according to requirements, and the synthetic method has high repeatability and low production cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides macroporous carbon and a preparation method thereof.
The present invention provides, in a first aspect, a macroporous carbon material having the following features: the composition is amorphous carbon; the porous material comprises two stages of pore channels, wherein the pore diameter of a first stage pore channel is 50-1400 nm, the most probable pore diameter D of the first stage pore channel is 60-900nm, and the proportion of pores within 0.8D-1.2D in the whole first stage pore channel is more than 65%; the most probable pore size of the secondary pore passage is 2-5 nm; the total specific surface area is 500-1000 m2/g。
The second aspect of the present invention provides a method for preparing macroporous carbon, the method comprising:
(1) mixing a Beta molecular sieve with an acid solution, treating at 50-200 ℃ for 1-10 h, then carrying out solid-liquid separation, and washing and drying collected solids;
(2) mixing the Beta molecular sieve obtained in the step (1) with a sodium benzoate solution, uniformly mixing, carrying out solid-liquid separation, and drying the collected solid;
(3) uniformly mixing the Beta molecular sieve obtained after the treatment of the step (2), saccharides and water;
(4) drying the material obtained in the step (3) at 50-100 ℃ until the solution becomes viscous;
(5) carrying out high-temperature treatment on the material obtained in the step (4) in a nitrogen atmosphere;
(6) and (3) mixing the solid-phase material obtained in the step (5) with an alkali solution, treating for 1-10 h at 100-200 ℃, and then filtering, washing and drying to obtain the macroporous carbon.
In the method, the crystal size of the Beta molecular sieve is 70-1000 nm, and the Beta molecular sieve can be purchased from a commodity which meets the requirement and sold in the market, and can also be prepared according to the existing method.
In the method, the Beta molecular sieve can be prepared by the following steps: mixing an alkali source, a silicon source, an aluminum source, water and a template agent (TEAOH) according to a molar ratio of 3-8 Na2O：40～100SiO2：A12O3：800～1200H2O: and (3) uniformly mixing 10-30 TEAOH, then placing the mixture into a closed reactor, crystallizing the mixture for 10-60 hours at the temperature of 100-180 ℃, and finally separating, washing and drying the crystallized product to obtain the Beta molecular sieve.
In the above method, the inorganic base is sodium hydroxide; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride and aluminum nitrate; the silicon source is white carbon black and/or silica sol; the templating agent is tetraethylammonium hydroxide.
In the method, the crystallization reaction temperature is 100-180 ℃, the reaction time is 10-60 hours, the preferable reaction temperature is 105-160 ℃, and the reaction time is 20-50 hours.
In the method, the washing is washing by using distilled water; the drying condition is that the treatment is carried out for 5-15 h under the condition of 100-150 ℃, and preferably for 6-12 h under the condition of 110-140 ℃.
In the method, a pretreatment step (1A) is further included before the step (1), the Beta molecular sieve is firstly put into a screening solution, the Beta molecular sieve is naturally settled in the screening solution, when the molecular sieve is settled to the bottom of the screening solution, the screening solution is divided into a plurality of equal sections, such as n equal sections, and the value of n is an odd number larger than 1 (the value of n can be odd numbers such as 3, 5, 7, 9, 11, and the like). If the crystal size of the molecular sieve is relatively uniform, the value of n can be a smaller value, otherwise, a larger value is taken. When the molecular sieve is selected, the molecular sieves in different segments may be selected as required, and it is preferable to select the molecular sieve in the most central segment (for example, 1/3 in the middle when the molecular sieve is divided into three portions and 1/5 in the middle when the molecular sieve is divided into 5 portions), and the molecular sieve thus selected is filtered and dried.
In the method, the screening solution is any one of a propylene glycol aqueous solution and a glycerol aqueous solution, and the concentration of the screening solution is 5-75 wt%, preferably 10-70 wt%; the mass ratio of the screening solution to the Beta molecular sieve is 1-10: 1, preferably 2-8: 1.
In the method, any one of hydrochloric acid, nitric acid and sulfuric acid is selected as the acid in the step (1), and the concentration of the acid solution is 0.08-1.2 mol/L, preferably 0.1-1 mol/L. The liquid-solid mass ratio of the acid solution to the Beta molecular sieve is 1-10: 1, preferably 2-8: 1.
In the method, the treatment temperature in the step (1) is 50-200 ℃, and preferably 60-180 ℃; the treatment time is 1-10 h, preferably 2-8 h.
In the method, the concentration of the sodium benzoate solution in the step (2) is 2-20 wt%, preferably 3-18 wt%; the liquid-solid mass ratio of the sodium benzoate solution to the Beta molecular sieve is 1-10: 1, preferably 2-8: 1.
In the method, the solid-liquid separation in the step (1) and the step (2) is any technical means which can realize the solid-liquid separation in the field, for example, the solid material is separated from the liquid by adopting filtration, and the solid material is directly dried without washing.
In the method, the drying condition in the step (1) is treatment for 5-15 h at 100-150 ℃, preferably treatment for 6-12 h at 110-140 ℃.
In the method, the drying condition in the step (2) is treatment for 5-15 h at 100-150 ℃, preferably treatment for 6-12 h at 110-140 ℃.
In the method, the saccharide substance in the step (3) is one or more of sucrose and glucose.
In the method, the mass ratio of the Beta molecular sieve, the saccharides and the water in the step (3) is 0.1-2: 1: 10 to 33, preferably 0.2 to 1.8: 1: 12 to 30.
In the method, the treatment temperature of the high-temperature treatment in the step (5) is 700-1000 ℃, and preferably 750-900 ℃; the treatment time is 2-10 h, preferably 4-8 h.
In the method, the alkali liquor in the step (6) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and other solutions, and the concentration of the alkali liquor is 15-55 wt%, preferably 20-50 wt%; the mass ratio of the alkali liquor to the solid-phase material is 1-10: 1, and preferably 2-8: 1.
In the method, the treatment temperature in the step (6) is 120-180 ℃; the treatment time is 2-8 h.
In the method of the present invention, the washing in step (6) is washing with distilled water; the drying condition in the step (6) is that the treatment is carried out for 5-15 h under the condition of 100-150 ℃, and preferably for 6-12 h under the condition of 110-140 ℃.
In the method, the mixing in the step (1), the step (2) and the step (6) can adopt any one of stirring, high-speed shearing, ultrasonic treatment and the like, preferably under the ultrasonic condition, when the ultrasonic treatment is adopted, the treatment time is 10-60 min, preferably 15-55 min, the frequency of the ultrasonic wave is 15KHz-10MHz, and the power is 20-100W/L according to the volume of the solution.
The macroporous carbon provided by the invention has rich macropores, can be used as a catalyst carrier, an adsorbent and a chromatographic column filler, and can also be used as a synthetic template of an inorganic organic material.
Compared with the prior art, the macroporous carbon material and the preparation method thereof provided by the invention have the following advantages:
according to the preparation method, the Beta molecular sieve is treated by acid, then treated by sodium benzoate and then treated by ultrasonic treatment, so that under the comprehensive action of the treatment means, the Beta molecular sieve is more favorable for maintaining a monodispersed state, the molecular sieve is favorable for adsorbing a precursor substance on the outer surface of the Beta molecular sieve, the molecular sieve can be uniformly dispersed in a precursor solution, and the agglomeration of the molecular sieve and the phase separation of the molecular sieve and the precursor are avoided. Solves the technical problems that the macroporous carbon material can not be prepared and only the common microporous activated carbon can be obtained when the molecular sieve is agglomerated and the molecular sieve and the precursor are separated. According to the method, the macroporous carbon material prepared by using the Beta molecular sieve treated by sodium benzoate as the template has higher aperture concentration and more uniform aperture distribution, has more advantages in the separation field, and can finely control the screening of the separated substances according to the nanometer level.
In the preparation method, compared with other types of hard templates, the size of the template of the Beta molecular sieve can be accurately adjusted according to requirements, and the preparation method has high repeatability and low production cost.
Drawings
Fig. 1 is an SEM photograph of the macroporous carbon obtained in example 1.
Detailed Description
The macroporous carbon of the present invention and the preparation method thereof are described in detail below by way of specific examples, but are not limited thereto.
Example 1
(1) 0.44g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.7g of sodium aluminate was added thereto, and stirred for 30 min. Then 12g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized for 32 hours in an oven at the temperature of 140 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) And (2) putting the Beta molecular sieve obtained in the step (1) into 50 mL of 50wt% propylene glycol solution, naturally settling, taking out 1/3 part of the solution in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 12 h.
(3) Mixing the Beta molecular sieve obtained in the step (2) with 5mL of 0.5moL/L hydrochloric acid, loading the mixture into a closed reactor, treating the mixture for 5 hours at 100 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12 hours at 120 ℃.
(4) Mixing the Beta molecular sieve obtained in the step (3) with 5mL of 10wt% sodium benzoate solution, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 0.01MHz, and the power is 20W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(5) And (3) respectively adding 1g of the Beta molecular sieve obtained in the step (4) and 1g of cane sugar into 20mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 0.01MHz, and the power is 20W/L according to the volume of the solution.
(6) The resulting material of step (4) was dried at 80 ℃ until the solution became viscous.
(7) And (4) carrying out constant temperature treatment on the solid substance obtained in the step (5) at 780 ℃ for 5 h.
(8) And (3) mixing the substance obtained in the step (6) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon with the code of CL 1. The resulting sample is shown in FIG. 1 as macroporous carbon, with product properties shown in Table 1.
Example 2
(1) 0.11g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.7g of sodium aluminate was added thereto, and stirred for 30 min. Then 7g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized in an oven for 20 hours at 160 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) And (2) putting the Beta molecular sieve obtained in the step (1) into 50 mL of 70wt% propylene glycol solution, naturally settling the Beta molecular sieve, taking out 1/5 part of the solution in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 10 hours.
(3) Mixing the Beta molecular sieve obtained in the step (2) with 15mL of hydrochloric acid with the concentration of 1moL/L, loading the mixture into a closed reactor, treating the mixture for 8 hours at the temperature of 60 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12 hours at the temperature of 120 ℃.
(4) Mixing the Beta molecular sieve obtained in the step (3) with 5mL of 18wt% sodium benzoate solution, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.2MHz, and the power is 100W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(5) And (3) respectively adding 1.9g of the Beta molecular sieve obtained in the step (4) and 1g of cane sugar into 30mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min at the frequency of 1.2MHz and at the power of 100W/L according to the volume of the solution.
(6) The resultant material of step (5) was dried at 100 ℃ until the solution became viscous.
(7) And (4) treating the solid substance obtained in the step (6) at the constant temperature of 900 ℃ for 5 hours.
(8) And (3) mixing the substance obtained in the step (7) with 6mL of 50wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture at 180 ℃ for 2h, washing the obtained product with distilled water to be neutral, and drying the product at 120 ℃ for 12h to obtain macroporous carbon with the number of CL2, wherein the properties of the product are shown in Table 1.
Example 3
(1) 1.3 g of sodium hydroxide was dissolved in 30mL of 25wt% TEAOH and 15mL of distilled water, and stirred for 30 min. Then, 1g of sodium aluminate was added thereto, and stirred for 30 min. Then, 10g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized in an oven for 50 hours at the temperature of 105 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) And (2) putting the Beta molecular sieve obtained in the step (1) into 85mL of 10wt% propylene glycol solution, naturally settling, taking out 1/7 part solution in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 10 h.
(3) Mixing the Beta molecular sieve obtained in the step (2) with 5mL of 0.21moL/L hydrochloric acid, loading the mixture into a closed reactor, treating the mixture for 2 hours at 180 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12 hours at 120 ℃.
(4) Mixing the Beta molecular sieve obtained in the step (3) with 5mL of 10wt% sodium benzoate solution, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 0.9MHz, and the power is 50W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(5) And (3) respectively adding 0.27g of the Beta molecular sieve obtained in the step (4) and 1g of cane sugar into 20mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 0.9MHz, and the power is 150W/L according to the volume of the solution.
(6) The resultant material of step (5) was dried at 50 ℃ until the solution became viscous.
(7) And (4) carrying out constant temperature treatment on the solid substance obtained in the step (6) at 750 ℃ for 5 h.
(8) And (3) mixing the substance obtained in the step (7) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 8 hours at 120 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12 hours at 120 ℃ to obtain macroporous carbon with the number of CL3, wherein the properties of the product are shown in Table 1.
Example 4
(1) 0.24g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.7g of sodium aluminate was added thereto, and stirred for 30 min. Then 7g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized in an oven for 45 hours at the temperature of 120 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) And (2) putting the Beta molecular sieve obtained in the step (1) into 40mL of 35wt% propylene glycol solution, naturally settling, taking out 1/3 part solution in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 10 h.
(3) Mixing Beta molecular sieve with 10mL0.5 moL/L hydrochloric acid, loading into a closed reactor, treating at 100 ℃ for 4h, washing the obtained product with distilled water to neutrality, and drying at 120 ℃ for 12 h.
(4) Mixing the Beta molecular sieve obtained in the step (3) with 3mL of 13wt% sodium benzoate solution, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.3MHz, and the power is 36W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(5) And (3) respectively adding 0.5g of the Beta molecular sieve obtained in the step (4) and 1.2g of cane sugar into 25mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.3MHz, and the power is 36W/L according to the volume of the solution.
(6) The resulting material of step (5) was dried at 75 ℃ until the solution became viscous.
(7) And (4) carrying out constant temperature treatment on the solid substance obtained in the step (6) at 850 ℃ for 7 h.
(8) And (3) mixing the substance obtained in the step (7) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon with the number of CL4, wherein the properties of the product are shown in Table 1.
Example 5
(1) 1.28 g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.9 g of sodium aluminate was added thereto, and stirred for 30 min. Then 9g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized for 45 hours in an oven at 135 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) Putting the Beta molecular sieve obtained in the step (1) into 35mL of 50wt% propylene glycol solution, naturally settling, taking out the solution of 1/3 part in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 10 h.
(3) Mixing Beta molecular sieve with 13mL of 0.3moL/L hydrochloric acid, loading into a closed reactor, treating at 110 ℃ for 6h, washing the obtained product with distilled water to be neutral, and drying at 120 ℃ for 12 h.
(4) Mixing the Beta molecular sieve obtained in the step (3) with 5.5mL of 10wt% sodium benzoate solution, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1MHz, and the power is 32W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(5) And (3) respectively adding 0.85g of Beta molecular sieve obtained in the step (4) and 1g of cane sugar into 20mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1MHz, and the power is 32W/L according to the volume of the solution.
(6) The resulting material of step (5) was dried at 80 ℃ until the solution became viscous.
(7) And (4) treating the solid substance obtained in the step (6) at 850 ℃ for 5 h.
(8) And (3) mixing the substance obtained in the step (7) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon with the number of CL5, wherein the properties of the product are shown in Table 1.
Example 6
(1) 14.4g of commercial Beta molecular sieve (southern Kai university catalyst works) was placed in 50 mL of 50wt% propylene glycol solution and allowed to settle naturally, and when the molecular sieve just settled to the bottom, 1/3 part of the whole solution was taken out of the solution in the middle, filtered, and dried at 120 ℃ for 10 hours.
(2) Beta molecular sieve and 16mL of 0.7moL/L hydrochloric acid are mixed, the mixture is put into a closed reactor and treated for 2h at 70 ℃, then the obtained product is washed to be neutral by distilled water and then dried for 12h at 120 ℃.
(2) Mixing the Beta molecular sieve obtained in the step (1) with 17.5mL of 10wt% sodium benzoate solution, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1MHz, and the power is 32W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(3) And (3) respectively adding 0.8g of Beta molecular sieve obtained in the step (2) and 1g of cane sugar into 20mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1MHz, and the power is 32W/L according to the volume of the solution.
(4) The resulting material of step (3) was dried at 85 ℃ until the solution became viscous.
(5) And (4) treating the solid substance obtained in the step (4) at 855 ℃ for 5 h.
(6) And (3) mixing the substance obtained in the step (5) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon with the number of CL6, wherein the properties of the product are shown in Table 1.
Example 7
(1) 0.24g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.7g of sodium aluminate was added thereto, and stirred for 30 min. Then 7g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized in an oven for 45 hours at the temperature of 120 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) And (2) putting the Beta molecular sieve obtained in the step (1) into 40mL of 35wt% propylene glycol solution, naturally settling, taking out 1/3 part solution in the middle of the whole solution when the molecular sieve just settles to the bottom, filtering, and drying at 120 ℃ for 10 h.
(3) Mixing the Beta molecular sieve obtained in the step (2) with 10mL0.5 moL/L hydrochloric acid, loading into a closed reactor, treating for 4h at 100 ℃, washing the obtained product with distilled water to neutrality, and drying for 12h at 120 ℃.
(4) And (3) respectively adding 0.5g of Beta molecular sieve obtained in the step (3) and 1.2g of cane sugar into 25mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.3MHz, and the power is 36W/L according to the volume of the solution.
(5) The resulting material of step (4) was dried at 75 ℃ until the solution became viscous.
(6) And (4) carrying out constant temperature treatment on the solid substance obtained in the step (5) at 840 ℃ for 7 h.
(7) And (3) mixing the substance obtained in the step (6) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon, wherein the number of the macroporous carbon is CL 7, and the properties of the product are shown in Table 1.
Example 8
(1) 0.24g of sodium hydroxide was dissolved in 40mL of 25wt% TEAOH and 10mL of distilled water, and stirred for 30 min. Then, 0.7g of sodium aluminate was added thereto, and stirred for 30 min. Then 7g of white carbon black is slowly added and stirred for 30 min. Then the mixture is put into a closed reaction kettle and crystallized in an oven for 45 hours at the temperature of 120 ℃. Then washing the obtained product to be neutral by using distilled water, and then drying the product for 12h at the temperature of 120 ℃ to obtain the Beta molecular sieve.
(2) Mixing the Beta molecular sieve obtained in the step (1) with 10mL of 10mL0.5 moL/L hydrochloric acid, loading the mixture into a closed reactor, treating the mixture for 4 hours at 100 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12 hours at 120 ℃.
(3) Mixing the Beta molecular sieve obtained in the step (2) with 3mL of 13wt% sodium benzoate solution, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.3MHz, and the power is 36W/L according to the volume of the solution; then, after one filtration, the mixture is dried for 12 hours at the temperature of 120 ℃.
(4) And (3) respectively adding 0.5g of Beta molecular sieve obtained in the step (3) and 1.2g of cane sugar into 25mL of water, uniformly stirring, and carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 1.3MHz, and the power is 36W/L according to the volume of the solution.
(5) The resulting material of step (4) was dried at 75 ℃ until the solution became viscous.
(6) And (4) carrying out constant temperature treatment on the solid substance obtained in the step (5) at 840 ℃ for 7 h.
(7) And (3) mixing the substance obtained in the step (6) with 5mL of 40wt% NaOH solution, loading the mixture into a closed reactor, treating the mixture for 7h at 150 ℃, washing the obtained product to be neutral by using distilled water, and drying the product for 12h at 120 ℃ to obtain macroporous carbon, wherein the number of the macroporous carbon is CL 8, and the properties of the product are shown in Table 1.
Comparative example 1
Adding 1g of sucrose into 20mL of water, stirring uniformly, carrying out ultrasonic treatment for 20min, wherein the frequency of ultrasonic waves is 0.01MHz, and the power is 20W/L according to the volume of the solution; drying at 80 deg.C until the solution becomes viscous; then processing for 5h at the constant temperature of 800 ℃; then mixing with 5mL of 40wt% NaOH solution, loading into a closed reactor, treating at 150 ℃ for 7h, washing the obtained product with distilled water to neutrality, and drying at 120 ℃ for 12h to obtain carbon material, wherein the number of the carbon material is CL9, and the properties of the product are shown in Table 1.
TABLE 1 physicochemical Properties of samples obtained in examples and comparative examples
The concentration ratio of macropores is the proportion of macropores in plus or minus 20% (0.8D-1.2D) of the most probable pore diameter of macropores in the total macropores. The results of the examples and the comparative examples show that the method can prepare high-quality macroporous carbon without adopting the operation steps of the invention, and the carbon material prepared under the condition of the same material proportion is a common microporous carbon material and does not contain a macroporous structure.
Claims (31)
1. A preparation method of macroporous carbon comprises the following steps:
(1) mixing a Beta molecular sieve with an acid solution, treating at 50-200 ℃ for 1-10 h, then carrying out solid-liquid separation, and washing and drying collected solids;
(2) mixing the Beta molecular sieve obtained in the step (1) with a sodium benzoate solution, uniformly mixing, carrying out solid-liquid separation, and drying the collected solid;
(3) uniformly mixing the Beta molecular sieve obtained after the treatment of the step (2), saccharides and water;
(4) drying the material obtained in the step (3) at 50-100 ℃ until the solution becomes viscous;
(5) carrying out high-temperature treatment on the material obtained in the step (4) in a nitrogen atmosphere;
(6) and (3) mixing the solid-phase material obtained in the step (5) with an alkali solution, treating for 1-10 h at 100-200 ℃, and then filtering, washing and drying to obtain the macroporous carbon.
2. The method according to claim 1, wherein step (1) is preceded by a pretreatment step (1A) of first putting said Beta zeolite into a screening solution, allowing the Beta zeolite to settle naturally in the screening solution, dividing the screening solution into n equal sections when the zeolite settles to the bottom of the screening solution, where n is an odd number greater than 1, selecting molecular sieves in different sections as required when screening the molecular sieves, and filtering and drying the screened molecular sieves.
3. The method according to claim 2, wherein the molecular sieve is selected by selecting the molecular sieve in the most central region as required and filtering and drying the molecular sieve thus selected.
4. The method according to claim 2 or 3, wherein the screening solution is any one of an aqueous propylene glycol solution and an aqueous glycerol solution.
5. The method according to claim 2, wherein the concentration of the screening solution is 5-75 wt%, and the mass ratio of the screening solution to the Beta molecular sieve is 1-10: 1.
6. The method according to claim 2 or 5, wherein the concentration of the sieving solution is 10 to 70 wt%; the mass ratio of the screening solution to the Beta molecular sieve is 2-8: 1.
7. The method according to claim 1, wherein the acid in step (1) is any one of hydrochloric acid, nitric acid and sulfuric acid.
8. The method according to claim 1, wherein the acid concentration in the step (1) is 0.08-1.2 mol/L, and the solid-to-liquid mass ratio of the acid solution to the Beta molecular sieve is 1-10: 1.
9. The method according to claim 1 or 8, wherein the acid concentration in the step (1) is 0.1 to 1.0 mol/L; the liquid-solid mass ratio of the acid solution to the Beta molecular sieve is 2-8: 1.
10. The method according to claim 1, wherein the concentration of the sodium benzoate solution in the step (2) is 2-20 wt%, and the liquid-solid mass ratio of the sodium benzoate solution to the Beta molecular sieve is 1-10: 1.
11. The method according to claim 1 or 10, wherein the concentration of the sodium benzoate solution in the step (2) is 3 to 18 wt%; the liquid-solid mass ratio of the sodium benzoate solution to the Beta molecular sieve is 2-8: 1.
12. The method according to claim 1, wherein the drying condition in the step (2) is 100 to 150 ℃ for 5 to 15 hours.
13. The method according to claim 1 or 12, wherein the drying condition in the step (2) is treatment at 110 to 140 ℃ for 6 to 12 hours.
14. The method according to claim 1, wherein the saccharide in step (3) is one or more of sucrose and glucose.
15. The method according to claim 1, wherein the mass ratio of the Beta molecular sieve, the saccharides and the water in the step (3) is 0.1-2: 1: 10 to 33.
16. The method according to claim 2, wherein the mass ratio of the Beta molecular sieve, the saccharides and the water in the step (3) is 0.2-1.8: 1: 12 to 30.
17. The method according to claim 1, wherein the high-temperature treatment in the step (5) is carried out at a treatment temperature of 700 to 1000 ℃ for 2 to 10 hours.
18. The method according to claim 1 or 17, wherein the treatment temperature of the high-temperature treatment in the step (5) is 750 to 900 ℃; the treatment time is 4-8 h.
19. The method according to claim 1, wherein the alkali liquor in the step (6) is one or more of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution, the concentration of the alkali liquor is 15-55 wt%, and the mass ratio of the alkali liquor to the solid-phase material is 1-10: 1.
20. The method according to claim 1 or 19, wherein the alkali liquor in the step (6) is one or more of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution, and the concentration of the alkali liquor is 20-50 wt%; the mass ratio of the alkali liquor to the solid-phase material is 2-8: 1.
21. The method according to claim 1, wherein the treatment temperature in the step (6) is 120 to 180 ℃; the treatment time is 2-8 h.
22. The method according to claim 1, wherein the washing in step (6) is washing with distilled water; the drying condition in the step (6) is that the treatment is carried out for 5-15 h at the temperature of 100-150 ℃.
23. The method according to claim 22, wherein the drying condition in the step (6) is 110 to 140 ℃ for 6 to 12 hours.
24. The process according to claim 2, wherein said Beta molecular sieve is prepared by: alkali source, silicon source, aluminum source, water and template agent TEAOH according to the molar ratio of 3-8 Na2O：40～100SiO2：A12O3：800～1200H2O: and (3) uniformly mixing 10-30 TEAOH, then placing the mixture into a closed reactor, crystallizing the mixture for 10-60 hours at the temperature of 100-180 ℃, and finally separating, washing and drying the crystallized product to obtain the Beta molecular sieve.
25. The method of claim 24, wherein the alkali source is sodium hydroxide; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride and aluminum nitrate; the silicon source is white carbon black and/or silica sol; the templating agent is tetraethylammonium hydroxide.
26. The method as claimed in claim 24, wherein the crystallization reaction temperature is 100 to 180 ℃ and the reaction time is 10 to 60 hours.
27. The method according to claim 24 or 26, wherein the crystallization reaction temperature is 105 to 160 ℃ and the reaction time is 20 to 50 hours.
28. The method of claim 24, wherein the washing is with distilled water; the drying condition is that the treatment is carried out for 5-15 hours at the temperature of 100-150 ℃.
29. The method according to claim 28, wherein the drying is carried out at 110-140 ℃ for 6-12 h.
30. A macroporous carbon material, wherein the macroporous carbon material is prepared using the method of any one of claims 1-29.
31. The macroporous carbon material of claim 30, wherein the carbon material has the following characteristics: the composition is amorphous carbon; the porous material comprises two stages of pore channels, wherein the pore diameter of a first stage pore channel is 50-1400 nm, the most probable pore diameter D of the first stage pore channel is 60-1000nm, and the proportion of pores within 0.8D-1.2D in the whole first stage pore channel is more than 65%; the most probable pore size of the secondary pore passage is 2-5 nm; the total specific surface area is 500-1000 m2/g。
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| CN105621383A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of macroporous carbon |
| CN105621411A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Method for synthesizing macroporous carbon material |
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| CN105621383A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method of macroporous carbon |
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