Preparation method of micropore-rich highly-graphitized deodorizing powder carbon

Abstract

The invention discloses a preparation method of micropore-rich highly-graphitized deodorizing powder carbon, and belongs to the technical field of activated carbon materials. The method comprises the following steps: by taking anthracite as a raw material, carrying out deliming by hydrochloric acid and hydrofluoric acid, carrying out modification pretreatment by tricresyl phosphate and tetraisobutyl titanate, dipping in a potassium ferrate solution, and sequentially carrying out carbonization and water vapor activation under the protection of nitrogen, so as to finally prepare the activated carbon with high micropore volume and high graphitization degree. The potassium ferrate is used as a catalyst to synchronously promote the potassium hydroxide activation reaction and the iron-based graphitization process. The method is simple in process and low in cost, the obtained material has excellent adsorbability and stability, the adsorption capacity of 2-methylisoborneol and geosmin is remarkably improved, and the method is suitable for efficiently removing odor substances of a drinking water source.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of activated carbon materials, and particularly relates to a preparation method of micropore-rich high-graphitized odor-removing powdered carbon. BACKGROUND

[0002] Activated carbon has rich pore structure and adjustable chemical and crystal properties, which can be targetedly regulated through raw material selection, preparation conditions and processes. In recent years, graphitized porous carbon with high crystalline carbon texture has attracted much attention due to its chemical stability and high adsorption performance. Studies have shown that improving the surface hydrophobicity of activated carbon can significantly improve the adsorption performance of small molecular nonpolar organic molecules. In addition, studies have also shown the importance of micropores of activated carbon for the adsorption of some odor substances, and have taken it as an important indicator for screening or preparing activated carbon, which provides a direction for further targeted preparation of high-performance carbon materials. The existing preparation methods of graphitized ordered porous carbon materials, such as the sacrificial template method using silica or surfactants, are expensive in precursor and complex in steps, which limits its large-scale production and further development, and it is difficult to form a dense microporous structure by the conventional template method. Therefore, it is urgent to develop a low-cost, simple and effective method to prepare activated carbon with both graphitization and micropore-rich characteristics.

[0003] Coal is often used as a raw material for activated carbon, and anthracite has high aromaticity and is considered as the main precursor of natural graphite. The preparation process of graphitized porous carbon material includes carbonization, activation and graphitization. After activating the raw material through the carbonization step, physical activation and chemical activation methods can be used to further develop the porosity, pore size distribution and specific surface area of the carbonized material to achieve a developed pore structure. However, the preparation of graphitized porous carbon often involves complex steps, and the carbon material produced, although having a graphitic microstructure, has a low specific surface area, usually less than 1000 m 2 / g, which limits its application as a high-performance adsorbent. In addition, the structure of high-graphitized material is easy to cause the collapse of the carbon material skeleton, making it difficult to form rich pore characteristics.

[0004] Therefore, it is necessary to optimize the preparation method and process in combination with the existing activated carbon production process to provide a new way for the targeted preparation of high-efficiency odor-removing activated carbon. SUMMARY

[0005] The purpose of the present application is to provide a micropore-rich high-graphitized odor-removing powdered carbon with excellent adsorption performance, rich micropore structure and graphitized structure.

[0006] The technical scheme adopted by the present application to achieve the above purpose is as follows: A micropore-rich high-graphitized odor-removing powdered carbon is composed of a graphitized carbon skeleton, has micropores, and the surface is distributed with iron and potassium elements, wherein, The graphitization degree of the graphitized carbon skeleton is 20%-50%, The micropores are composed of microdomains, and the volume of the micropores is 0.25-0.5 cm 3 The average diameter of the microdomains is 4-6 nm, The microdomains include small-size microdomains and large-size microdomains, the diameter of the small-size microdomains is 1-4 nm, the diameter of the large-size microdomains is 4-10 nm, and the proportion of the large-size microdomains in the microdomains is 60-90%.

[0007] The iron-carbon composite is embedded in the graphitized carbon skeleton, and the crystal face diffraction peak of the graphitized carbon skeleton is 26.0°-26.2°.

[0008] A preparation method of a microporous high-graphitized deodorizing powder carbon, comprising the following preparation steps: The raw coal is subjected to ash removal and modification treatment to obtain pretreated raw coal, The pretreated raw coal is impregnated in a potassium ferrate solution, and then carbonization and activation are performed to obtain an activated carbon material.

[0009] Preferably, the solution used for ash removal comprises a hydrochloric acid solution and a hydrofluoric acid solution, and the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution is 0.2-2:0.2-2.

[0010] Preferably, the reagent used for modification comprises o-phosphoric acid trimethyl phenyl ester and titanium acid tetraisobutyl ester, and the mass ratio of the titanium acid tetraisobutyl ester to the o-phosphoric acid trimethyl phenyl ester is 2-20:3-30. The o-phosphoric acid trimethyl phenyl ester and the titanium acid tetraisobutyl ester participate in the modification process and interact with the ash-removed raw coal, and are more likely to form pores during thermal decomposition, thereby increasing the specific surface area and pore volume of the activated carbon and enhancing the adsorption capacity of the activated carbon for odor substances; during graphitization, the o-phosphoric acid trimethyl phenyl ester and the titanium acid tetraisobutyl ester promote the more orderly arrangement of the microdomains of the activated carbon material, optimize the microdomain structure, and improve the graphitization and stability of the activated carbon material.

[0011] Preferably, the solution used for impregnation comprises a potassium ferrate solution, and the mass of the potassium ferrate solution is measured by the mass of the potassium ferrate therein, and the mass ratio of the potassium ferrate to the pretreated raw coal is 1-100 mg:20-2000 g.

[0012] More preferably, the reagent used for impregnation can also comprise ethylamine thiophene, and the mass ratio of the potassium ferrate to the ethylamine thiophene is 2.5-10:1-4. The nitrogen and sulfur heteroatoms of the ethylamine thiophene can participate in the structure of carbon, promote the orderly arrangement of carbon atoms, make the nucleation and growth of graphite layers more smooth, thereby improving the graphitization degree of the material; make the distribution of pores more uniform, promote the formation and development of micropores, increase the surface defect sites, and improve the adsorption selectivity of the material for polar odor substances. Preferably, the carbonization temperature is 550-650°C.

[0013] Preferably, the activation is steam activation, the activation temperature is 800-900℃, and the steam flow rate is 0.4-0.6 mL / min.

[0014] The use of the microporous high-graphitized deodorizing powder carbon in adsorbing odor substances, including 2-methylisoborneol and geosmin.

[0015] The application further provides a preparation method of the pretreated raw coal, comprising: The anthracite is selected as the raw coal, is firstly crushed and ground, is washed with deionized water, is dried at 100-110℃ for 10-15h after filtration to obtain a coal sample; the coal sample is mixed with a 4-6 mol / L hydrochloric acid solution, is magnetically stirred at 35-45℃ for 10-15h, and is subjected to a deashing treatment after filtration by adding a 15-20 mol / L hydrofluoric acid solution to the solid and magnetically stirring at 40℃ for 10-15h; and the deashing raw coal, i.e. the pretreated raw coal, is obtained by drying at 110-130℃ for 20-30h after washing with deionized water until F - and Cl - are not detected in the washing liquid.

[0016] Preferably, the particle size of the coal sample is 25-35 mesh.

[0017] Preferably, the mass-volume ratio of the coal sample to the hydrochloric acid solution is 15-150 g:0.2-2 L.

[0018] Preferably, the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution is 0.2-2:0.2-2.

[0019] The application further provides a preparation method of the activated carbon material, comprising: The pretreated raw coal is immersed in a potassium ferrate solution and continuously stirred for 6-10h, and a solid mixture is obtained by drying at 100-110℃ for 10-15h; the solid mixture is heated in a tube furnace under nitrogen protection, and carbonization is performed by keeping the furnace temperature at 550-650℃ for 0.5-1.5h after the furnace temperature reaches 550-650℃; then the temperature is continuously increased to 800-900℃, the nitrogen is closed, a water vapor generator is opened, and water vapor is introduced for 0.5-1.5h to perform activation; the water vapor generator is closed, and nitrogen is introduced again until the temperature in the tube furnace decreases to room temperature to obtain a carbon material; the carbon material is washed with a 1-3 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid is 6.9-7.1, and a microporous graphitized carbon, i.e. the activated carbon material, is obtained by drying at 100-110℃ for 10-15h.

[0020] Preferably, the mass of the potassium ferrate solution is measured by the mass of the potassium ferrate therein, and the mass ratio of the potassium ferrate to the pretreated raw coal is 1-100 mg:20-2000 g.

[0021] Preferably, the nitrogen flow rate is 150-250 mL / min, and the heating rate is 4-6 ℃ / min.

[0022] Preferably, the water vapor flow rate is 0.4-0.6 mL / min.

[0023] The present application also provides a preparation method of the pretreated raw coal, comprising: The anthracite is selected as the raw coal, and is first crushed and ground, washed with deionized water, filtered, and dried at 100-110 ℃ for 10-15 h to obtain a coal sample; the coal sample is mixed with a 4-6 mol / L hydrochloric acid solution, magnetically stirred at 35-45 ℃ for 10-15 h, and after filtration, 15-20 mol / L hydrofluoric acid solution is added to the solid, and magnetically stirred at 40 ℃ for 10-15 h for deashing treatment; the deashing raw coal is obtained by washing with deionized water until no F- and Cl- are detected in the washing liquid, and drying at 110-130 ℃ for 20-30 h; orthophosphoric acid trimethylphenyl ester and titanium acid tetraisobutyl ester are dissolved in ethanol, the pH is adjusted to 4.4-4.6 to obtain an ethanol mixture, the deashing raw coal is immersed in the ethanol mixture and continuously stirred for 10-15 h, washed with deionized water until the pH of the washing liquid is 6.9-7.1, and dried at 100-110 ℃ for 10-15 h to obtain the pretreated raw coal.

[0024] Preferably, the particle size of the coal sample is 25-35 mesh.

[0025] Preferably, the mass-volume ratio of the coal sample to the hydrochloric acid solution is 15-150 g:0.2-2 L.

[0026] Preferably, the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution is 0.2-2:0.2-2.

[0027] Preferably, the mass-volume ratio of the orthophosphoric acid trimethylphenyl ester to the ethanol is 2-20 g:0.2-2 L.

[0028] Preferably, the mass ratio of the titanium acid tetraisobutyl ester to the orthophosphoric acid trimethylphenyl ester is 2-20:3-30.

[0029] Preferably, the mass of the ethanol mixture is measured by the mass of the ethanol therein, and the mass-volume ratio of the deashing raw coal to the ethanol is 15-150 g:0.2-2 L.

[0030] The present application also provides a preparation method of the activated carbon material, comprising: The pretreated raw coal is immersed in a potassium ferrate solution, and ethylamine thiophene is added under stirring, and continuously stirred for 6-10 h, and dried at 100-110℃ for 10-15 h to obtain a solid mixture; the solid mixture is heated in a tube furnace under nitrogen protection, and after the furnace temperature reaches 550-650℃, it is kept for 0.5-1.5 h for carbonization; then it is continuously heated to 800-900℃, the nitrogen is closed and the water vapor generator is opened, and water vapor is introduced for 0.5-1.5 h for activation; the water vapor generator is closed and nitrogen is introduced again until the temperature in the tube furnace decreases to room temperature, to obtain a carbon material; the carbon material is washed with a 1-3 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid is 6.9-7.1, and dried at 100-110℃ for 10-15 h to obtain a microporous graphitized carbon, i.e. an activated carbon material.

[0031] Preferably, the mass of the potassium ferrate solution is measured by the mass of the potassium ferrate therein, and the mass ratio of the potassium ferrate to the pretreated raw coal is 1-100 mg:20-2000 g.

[0032] Preferably, the mass ratio of the potassium ferrate to the ethylamine thiophene is 2.5-10:1-4.

[0033] Preferably, the nitrogen flow rate is 150-250 mL / min, and the heating rate is 4-6℃ / min.

[0034] Preferably, the water vapor flow rate is 0.4-0.6 mL / min.

[0035] The present application has the following beneficial effects: the preparation method is simple, the steps and the complexity of the equipment are reduced, the prepared activated carbon material has excellent microporous structure, tap density and adsorption stability, and the adsorption capacity for 2-methylisoborneol and geosmin is significantly improved. Therefore, the present application is a preparation method of a microporous high-graphitized odor-removing powder carbon with excellent adsorption performance, rich microporous structure and graphitized structure. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 It is a schematic diagram of the preparation process of the activated carbon material.

[0037] Figure 2 It is a schematic diagram of the adsorption isotherm results of the activated carbon material for odor substances.

[0038] Figure 3 It is a schematic diagram of the scanning electron microscope of the activated carbon material.

[0039] Figure 4 It is a schematic diagram of the energy dispersive X-ray spectroscopy analysis of the activated carbon material.

[0040] Figure 5 A schematic diagram of pore size distribution of activated carbon material.

[0041] Figure 6 A schematic diagram of X-ray diffraction spectrum of activated carbon material.

[0042] Figure 7 A schematic diagram of graphitization mechanism of iron catalytic activated carbon material.

[0043] Figure 8 A schematic diagram of atomic force microscope of activated carbon material.

[0044] Figure 9 A schematic diagram of particle size distribution of activated carbon material.

[0045] Figure 10 A schematic diagram of mechanism of carbon material structure development based on micro-domain theory. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0047] The concepts involved in the present application will be described below in combination with the drawings. It should be noted that the following descriptions of the concepts are only for the purpose of making the content of the present application easier to understand, and do not represent a limitation on the scope of protection of the present application; meanwhile, the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the drawings and in combination with the embodiments.

[0048] Embodiment 1: Preparation of pretreated raw coal: anthracite was selected as raw coal, which was first crushed and ground, washed with deionized water, filtered, and dried at 105℃ for 12h to obtain a coal sample; the coal sample was mixed with 5mol / L hydrochloric acid solution, magnetically stirred at 40℃ for 12h, and then filtered; 16.5mol / L hydrofluoric acid solution was added to the solid, magnetically stirred at 40℃ for 12h, and then filtered; the solid was washed with deionized water until no F - and Cl - were detected in the washing liquid; and the solid was dried at 120℃ for 24h to obtain the deashed raw coal, i.e., the pretreated raw coal. The particle size of the coal sample was 30 mesh, the mass-volume ratio of the coal sample to the hydrochloric acid solution was 75g:1L, and the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution was 1:1.

[0049] Preparation of the activated carbon material: the pretreated raw coal was immersed in a potassium ferrate solution and continuously stirred for 8 h, and then dried at 105°C for 12 h to obtain a solid mixture; the solid mixture was heated in a tube furnace under nitrogen protection, and carbonization was performed by keeping the furnace temperature at 600°C for 1 h; then the temperature was continuously increased to 850°C, the nitrogen was turned off and a water vapor generator was turned on, and water vapor was introduced for 1 h for activation; the water vapor generator was turned off and nitrogen was introduced again until the temperature in the tube furnace decreased to room temperature, to obtain a carbon material; the carbon material was washed with a 2 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid was 7.0, and then dried at 105°C for 12 h to obtain a microporous-rich graphitized carbon, i.e., the activated carbon material. The mass of the potassium ferrate solution was measured based on the mass of potassium ferrate therein, the mass ratio of potassium ferrate to the pretreated raw coal was 5 mg: 100 g, the nitrogen flow rate was 200 mL / min, the heating rate was 5°C / min, and the water vapor flow rate was 0.5 mL / min.

[0050] Example 2: Compared with Example 1, the only difference is the preparation of the activated carbon material.

[0051] Preparation of the activated carbon material: the pretreated raw coal was immersed in a potassium ferrate solution and continuously stirred for 8 h, and then dried at 105°C for 12 h to obtain a solid mixture; the solid mixture was heated in a tube furnace under nitrogen protection, and carbonization was performed by keeping the furnace temperature at 600°C for 1 h; then the temperature was continuously increased to 850°C, the nitrogen was turned off and a water vapor generator was turned on, and water vapor was introduced for 1 h for activation; the water vapor generator was turned off and nitrogen was introduced again until the temperature in the tube furnace decreased to room temperature, to obtain a carbon material; the carbon material was washed with a 2 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid was 7.0, and then dried at 105°C for 12 h to obtain a microporous-rich graphitized carbon, i.e., the activated carbon material. The mass of the potassium ferrate solution was measured based on the mass of potassium ferrate therein, the mass ratio of potassium ferrate to the pretreated raw coal was 0.2 mg: 1 g, the nitrogen flow rate was 200 mL / min, the heating rate was 5°C / min, and the water vapor flow rate was 0.5 mL / min.

[0052] Example 3: Compared with Example 1, the only difference is the preparation of the activated carbon material.

[0053] Preparation of the activated carbon material: the pretreated raw coal was immersed in a potassium ferrate solution and continuously stirred for 8 h, and then dried at 105°C for 12 h to obtain a solid mixture; the solid mixture was heated in a tube furnace under nitrogen protection, and after the furnace temperature reached 600°C, carbonization was performed by keeping the temperature for 1 h; then the temperature was continuously increased to 850°C, the nitrogen was closed and the water vapor generator was opened, and water vapor was introduced for 1 h for activation; the water vapor generator was closed and nitrogen was introduced again until the temperature in the tube furnace decreased to room temperature, to obtain a carbon material; the carbon material was washed with a 2 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid was 7.0, and then dried at 105°C for 12 h to obtain a micropore-rich graphitized carbon, i.e. the activated carbon material. The mass of the potassium ferrate solution was measured based on the mass of potassium ferrate therein, the mass ratio of potassium ferrate to the pretreated raw coal was 0.5 mg: 1 g, the nitrogen flow rate was 200 mL / min, the heating rate was 5°C / min, and the water vapor flow rate was 0.5 mL / min.

[0054] Example 4: Compared with Example 1, the only difference is the preparation of the pretreated raw coal.

[0055] The preparation process of the activated carbon prepared in this example is shown in Figure 1 , which includes: the raw coal was crushed and then immersed in an ethanol mixed solution to obtain a pretreated raw coal, the ethanol mixed solution including o-phosphoric acid trimethylphenyl ester and titanium acid tetraisobutyl ester; the pretreated raw coal was immersed in a potassium ferrate solution and then carbonized under nitrogen protection, activated in water vapor and catalytically graphitized to obtain an activated carbon material.

[0056] Preparation of the pretreated raw coal: anthracite was selected as the raw coal, which was first crushed, ground, washed with deionized water, filtered and then dried at 105°C for 12 h to obtain a coal sample; the coal sample was mixed with a 5 mol / L hydrochloric acid solution, magnetically stirred at 40°C for 12 h, and then filtered, and 16.5 mol / L hydrofluoric acid solution was added to the solid, magnetically stirred at 40°C for 12 h, and then washed with deionized water until no F - and Cl -The ash-removed raw coal was obtained by drying at 120°C for 24h; the o-phosphoric acid trimethyl phenyl ester and the titanium acid tetraisobutyl ester were dissolved in ethanol, and the pH was adjusted to 4.5 to obtain an ethanol mixture; the ash-removed raw coal was immersed in the ethanol mixture and continuously stirred for 12h; the coal sample was washed with deionized water until the pH of the washing liquid was 7.0; and the pretreated raw coal was obtained by drying at 105°C for 12h. The particle size of the coal sample was 30 mesh, the mass-volume ratio of the coal sample to the hydrochloric acid solution was 75g:1L, the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution was 1:1, the mass-volume ratio of the o-phosphoric acid trimethyl phenyl ester to ethanol was 10g:1L, the mass ratio of the titanium acid tetraisobutyl ester to the o-phosphoric acid trimethyl phenyl ester was 10:15, the mass of the ethanol mixture was measured by the mass of ethanol therein, and the mass-volume ratio of the ash-removed raw coal to ethanol was 75g:1L.

[0057] Example 5: The difference between this example and Example 1 is only in the preparation of the pretreated raw coal.

[0058] Preparation of the pretreated raw coal: The anthracite was selected as the raw coal, which was first crushed, ground, washed with deionized water, filtered, and dried at 105°C for 12h to obtain a coal sample; the coal sample was mixed with a 5mol / L hydrochloric acid solution, magnetically stirred at 40°C for 12h, and then 16.5mol / L hydrofluoric acid solution was added to the solid, which was magnetically stirred at 40°C for 12h; the coal sample was washed with deionized water until no F - and Cl - The ash-removed raw coal was obtained by drying at 120°C for 24h; the o-phosphoric acid trimethyl phenyl ester and the titanium acid tetraisobutyl ester were dissolved in ethanol, and the pH was adjusted to 4.5 to obtain an ethanol mixture; the ash-removed raw coal was immersed in the ethanol mixture and continuously stirred for 12h; the coal sample was washed with deionized water until the pH of the washing liquid was 7.0; and the pretreated raw coal was obtained by drying at 105°C for 12h. The particle size of the coal sample was 30 mesh, the mass-volume ratio of the coal sample to the hydrochloric acid solution was 75g:1L, the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution was 1:1, the mass-volume ratio of the o-phosphoric acid trimethyl phenyl ester to ethanol was 20g:1L, the mass ratio of the titanium acid tetraisobutyl ester to the o-phosphoric acid trimethyl phenyl ester was 10:15, the mass of the ethanol mixture was measured by the mass of ethanol therein, and the mass-volume ratio of the ash-removed raw coal to ethanol was 75g:1L.

[0059] Example 6: The difference between this example and Example 1 is only in the preparation of the activated carbon material.

[0060] Preparation of the activated carbon material: the pretreated raw coal was impregnated in a potassium ferrate solution, and ethylamine thiophene was added under stirring, continuously stirred for 8 h, and dried at 105°C for 12 h to obtain a solid mixture; the solid mixture was heated in a tube furnace under nitrogen protection, kept at 600°C for 1 h for carbonization after the furnace temperature reached 600°C, and then heated to 850°C, closed the nitrogen and opened the water vapor generator, and passed in water vapor for 1 h for activation; the water vapor generator was closed and nitrogen was passed in again until the temperature in the tube furnace dropped to room temperature to obtain a carbon material; the carbon material was washed with a 2 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid was 7.0, and dried at 105°C for 12 h to obtain a micropore-rich graphitized carbon, i.e., the activated carbon material. The mass of the potassium ferrate solution was measured based on the mass of potassium ferrate therein, the mass ratio of potassium ferrate to the pretreated raw coal was 5 mg: 100 g, the mass ratio of potassium ferrate to ethylamine thiophene was 5:2, the nitrogen flow rate was 200 mL / min, the heating rate was 5°C / min, and the water vapor flow rate was 0.5 mL / min.

[0061] Example 7: This example is compared with Example 1, and the only difference is the preparation of the activated carbon material.

[0062] Preparation of the activated carbon material: the pretreated raw coal was impregnated in a potassium ferrate solution, and ethylamine thiophene was added under stirring, continuously stirred for 8 h, and dried at 105°C for 12 h to obtain a solid mixture; the solid mixture was heated in a tube furnace under nitrogen protection, kept at 600°C for 1 h for carbonization after the furnace temperature reached 600°C, and then heated to 850°C, closed the nitrogen and opened the water vapor generator, and passed in water vapor for 1 h for activation; the water vapor generator was closed and nitrogen was passed in again until the temperature in the tube furnace dropped to room temperature to obtain a carbon material; the carbon material was washed with a 2 mol / L hydrochloric acid solution, and then washed with deionized water until the pH value of the washing liquid was 7.0, and dried at 105°C for 12 h to obtain a micropore-rich graphitized carbon, i.e., the activated carbon material. The mass of the potassium ferrate solution was measured based on the mass of potassium ferrate therein, the mass ratio of potassium ferrate to the pretreated raw coal was 5 mg: 100 g, the mass ratio of potassium ferrate to ethylamine thiophene was 5:2, the nitrogen flow rate was 200 mL / min, the heating rate was 5°C / min, and the water vapor flow rate was 0.5 mL / min.

[0063] Comparative Example 1: This comparative example is compared with Example 1, and the only difference is the preparation of the activated carbon material.

[0064] Preparation of the activated carbon material: the pretreated raw coal was heated in a tube furnace under nitrogen protection, carbonization was carried out after the furnace temperature reached 600℃ for 1 h, and the carbon material was obtained after the temperature decreased to room temperature; the carbon material was washed with 2 mol / L hydrochloric acid solution, then washed with deionized water until the pH value of the washing liquid was 7.0, and dried at 105℃ for 12 h to obtain the activated carbon material. The nitrogen flow rate was 200 mL / min, and the heating rate was 5℃ / min.

[0065] Comparative Example 2: This comparative example is compared with Example 1, and the only difference is the preparation of the activated carbon material.

[0066] Preparation of the activated carbon material: the pretreated raw coal was heated in a tube furnace under nitrogen protection, carbonization was carried out after the furnace temperature reached 600℃ for 1 h; then continue to heat to 850℃, close the nitrogen and open the water vapor generator, and pass in water vapor for 1 h for activation, to obtain the carbon material; the carbon material was washed with 2 mol / L hydrochloric acid solution, then washed with deionized water until the pH value of the washing liquid was 7.0, and dried at 105℃ for 12 h to obtain the activated carbon material. The nitrogen flow rate was 200 mL / min, the heating rate was 5℃ / min, and the water vapor flow rate was 0.5 mL / min.

[0067] Comparative Example 3: This comparative example is compared with Example 1, and the only difference is the preparation of the pretreated raw coal.

[0068] Preparation of the pretreated raw coal: anthracite was selected as the raw coal, which was first crushed, ground, washed with deionized water, filtered, and then dried at 105℃ for 12 h to obtain the coal sample; the coal sample was mixed with 5 mol / L hydrochloric acid solution, magnetically stirred at 40℃ for 12 h, and then filtered; 16.5 mol / L hydrofluoric acid solution was added to the solid, magnetically stirred at 40℃ for 12 h, and then washed with deionized water until no F - and Cl - were detected in the washing liquid, and then dried at 120℃ for 24 h to obtain the deashed raw coal; o-phenyl phenyl phosphate was dissolved in ethanol, the pH was adjusted to 4.5 to obtain an ethanol solution, the deashed raw coal was immersed in the ethanol solution and continuously stirred for 12 h, washed with deionized water until the pH of the washing liquid was 7.0, and then dried at 105℃ for 12 h to obtain the pretreated raw coal. The particle size of the coal sample was 30 mesh, the mass-volume ratio of the coal sample to the hydrochloric acid solution was 75 g:1 L, the volume ratio of the hydrofluoric acid solution to the hydrochloric acid solution was 1:1, the mass-volume ratio of o-phenyl phenyl phosphate to ethanol was 10 g:1 L, the mass of the ethanol solution was measured by the mass of ethanol therein, and the mass-volume ratio of the deashed raw coal to ethanol was 75 g:1 L.

[0069] Comparative Example 4: This comparative example is compared with Example 1, and the only difference is the preparation of the pretreated raw coal.

[0070] Preparation of pretreated raw coal: Anthracite was selected as the raw coal. It was first crushed and ground, washed with deionized water, filtered, and dried at 105℃ for 12 hours to obtain a coal sample. The coal sample was mixed with a 5 mol / L hydrochloric acid solution and magnetically stirred at 40℃ for 12 hours. After filtration, a 16.5 mol / L hydrofluoric acid solution was added to the solid, and the mixture was magnetically stirred at 40℃ for 12 hours. The solid was then washed with deionized water until no F was detected in the washing solution. - and Cl - The deashed raw coal was obtained by drying at 120℃ for 24 hours. Tetraisobutyl titanate was dissolved in ethanol, and the pH was adjusted to 4.5 to obtain an ethanol solution. The deashed raw coal was immersed in the ethanol solution and stirred continuously for 12 hours. It was then washed with deionized water until the pH of the washing solution reached 7.0, and dried at 105℃ for 12 hours to obtain pretreated raw coal. The particle size of the coal sample was 30 mesh. The mass-to-volume ratio of coal sample to hydrochloric acid solution was 75 g:1 L, the volume ratio of hydrofluoric acid solution to hydrochloric acid solution was 1:1, the mass-to-volume ratio of tetraisobutyl titanate to ethanol was 15 g:1 L, and the mass of the ethanol solution was measured by the mass of ethanol contained within it. The mass-to-volume ratio of deashed raw coal to ethanol was 75 g:1 L.

[0071] Experimental Example 1: Test on the adsorption effect of activated carbon materials on odor substances.

[0072] Test samples: Activated carbon materials prepared in Examples 1-3 and Comparative Example 2.

[0073] Test method: 2-Methylisoborneol and geosmin standard substances were dissolved in deionized water or Taihu Lake water to prepare 500 ng / L 2-methylisoborneol and geosmin solutions, respectively. Activated carbon material was ground, sieved, and dispersed in deionized water to prepare a 4.0 g / L activated carbon stock solution, which was stored overnight to ensure complete wetting. Two hours before the experiment, the activated carbon stock solution was stirred at 400 rpm on a magnetic stirrer until the PAC addition was complete, with stirring during addition to ensure proper dosing. The concentration of the activated carbon stock solution was uniform during the process. A predetermined amount of activated carbon material was added to each of two glass conical flasks containing 250 mL of 2-methylisoborneol solution and geosmin solution, respectively. The flasks were shaken at 25°C for 48 hours to conduct an adsorption isotherm experiment. After standing, the supernatant was collected, filtered through a 0.45 μm membrane filter, and 100 ng / L of 2-isopropyl-3-methoxypyrazine was added as an internal standard. After enrichment and pretreatment using solid-phase microextraction, the solution was analyzed by gas chromatography-mass spectrometry.

[0074] The adsorption isotherm of the activated carbon material prepared by this invention for odor substances is as follows: Figure 2 As shown, where Figure 2 (a) Schematic diagram of the adsorption results of 2-methylisoborneol under deionized water background. Figure 2(b) is a schematic diagram of adsorption results of geosmin in the background of deionized water, Figure 2 (c) is a schematic diagram of adsorption results of 2-methylisoborneol in the background of water source in Taihu Basin, Figure 2 (d) is a schematic diagram of adsorption results of geosmin in the background of water source in Taihu Basin. The adsorption of 2-methylisoborneol solution and geosmin can be well simulated by the Freundlich isotherm model, and the q 10 , i.e. the equilibrium adsorption capacity when Ce is 10 ng / L, to evaluate the adsorption capacity of the activated carbon material. Compared with the comparative example 2 using only water vapor activation, the adsorption capacity of examples 1-3 for 2-methylisoborneol and geosmin is significantly improved; under the background conditions of water source in Taihu Basin, the adsorption capacity of examples 1-3 also shows a substantial increase, and the increase of 2-methylisoborneol adsorption capacity is slightly weaker than that of geosmin, which is related to the difference in hydrophobicity between them, where 2-methylisoborneol has slightly higher polarity and lower octanol / water partition coefficient, resulting in it being more difficult to be removed by adsorption than geosmin.

[0075] Test Example 2: Microstructure characterization of the activated carbon material.

[0076] Test sample: activated carbon materials prepared by examples 2, comparative example 1 and comparative example 2.

[0077] Test method: scanning electron microscopy is performed on the activated carbon material to obtain the microstructure characteristics of the sample, and energy dispersive X-ray analysis is performed on the activated carbon material prepared by example 2.

[0078] The scanning electron micrograph of the activated carbon material prepared by the present application is shown in Figure 3 , wherein Figure 3 (a) is a schematic diagram of the results of comparative example 1, Figure 3 (b) is a schematic diagram of the results of comparative example 2, Figure 3 (c) is a schematic diagram of the results of example 2. As can be seen from the figure, the surface of comparative example 1 is relatively rough, and the strong acidity of hydrochloric acid and hydrofluoric acid dissolved the ash minerals in the coal during the ash removal process, and the removal of ash particles from the carbon matrix resulted in a rough surface of the coal particles; comparative example 2 obtained by using only water vapor activation can be observed to have a rough surface and newly generated pores; after adding potassium ferrate for auxiliary activation, the carbon particle surface of example 2 becomes quite smooth, like graphene, smooth and wrinkled.

[0079] The energy dispersive X-ray of the activated carbon material prepared by the present application is shown in Figure 4 , wherein Figure 4 (a) is a schematic diagram of the microstructure of example 2, Figure 4 (b) is a schematic diagram of the distribution of carbon element of example 2, Figure 4 (c) is a schematic diagram of the distribution of oxygen element of example 2,Figure 4 (d) is a distribution diagram of nitrogen element of Example 2, Figure 4 (e) is a distribution diagram of potassium element of Example 2, Figure 4 (f) is a distribution diagram of iron element of Example 2. As can be seen from the figure, the active carbon material prepared by the application is mainly composed of carbon element and oxygen element, and a small amount of potassium element and iron Fe element is due to the addition of potassium ferrate. The pickling and water washing steps after heat treatment can remove most of the reagents, but there is still a small amount of residual, especially the iron element may be wrapped in the carbon skeleton structure due to the catalytic graphitization process and is difficult to be washed out.

[0080] Test Example 3: Pore structure characterization of active carbon material.

[0081] Test sample: active carbon material prepared in Examples 1-3 and Comparative Examples 1-2.

[0082] Test method: scanning electron microscopy scanning of active carbon material to obtain pore structure characteristics of sample.

[0083] The pore structure characteristics of the active carbon material prepared by the application are shown in Figure 5 Table 1 shows the pore structure parameters of the active carbon material.

[0084] Table 1 Pore structure parameters of active carbon material Activated carbon material Specific surface area (m 2 / g)]]> Total pore volume (cm 3 / g) Micropore volume (cm 3 / g)]]> Mesopore volume (cm 3 / g) Comparative Example 1 354.37 0.15 0.11 0.01 Comparative Example 2 726.25 0.33 0.25 0.07 Example 1 853.86 0.35 0.32 0.03 Example 2 1279.76 0.51 0.43 0.07 Example 3 1009.20 0.43 0.38 0.05 The pickling step in the raw coal pretreatment of Comparative Example 1 removes the ash minerals in the carbon matrix, resulting in the generation of a small amount of pore structure; after the water vapor activation of Comparative Example 2, the pore structure is significantly developed; the addition of potassium ferrate for activation process further develops the pore structure of the examples, wherein the specific surface area and micropore volume of Example 2 are increased by 2.33 times and 2.91 times respectively compared with Comparative Example 1, and the micropore volume of Example 2 is increased by 72% compared with Comparative Example 2, and the pore volume has no obvious change, indicating that potassium ferrate has a good effect on the development of micropores.

[0085] Test Example 4: X-ray diffraction test of active carbon material.

[0086] Test sample: active carbon material prepared in Examples 1-3 and Comparative Examples 1-2.

[0087] Test method: dry active carbon material is ground into fine powder, evenly filled into the groove of the sample holder, and gently compacted with glass sheet and other tools to ensure that the sample is tightly attached to the sample holder. The scanning angle 2θ is set between 10°-90°, the scanning speed is set between 0.02°-0.05° / s, and the X-ray diffraction test is carried out to collect the diffraction spectrum.

[0088] The X-ray diffraction spectrum of the active carbon material prepared by the application is shown inFigure 6 X-ray quantitative analysis is shown in Table 2.

[0089] Table 2 X-ray quantitative analysis of activated carbon materials Activated carbon material Diffraction angle (°) Interplanar spacing (nm) Degree of graphitization (%) Comparative Example 1 26.0042 0.3424 18.9131 Comparative Example 2 25.9721 0.3428 14.0774 Example 1 26.0660 0.3416 28.1891 Example 2 26.1259 0.3408 37.1377 Example 3 26.1561 0.3404 41.6336 The diffraction patterns of Examples 1-3 all contain a strong peak centered at about 26.5°, corresponding to the (002) plane of graphite; compared with Example 1, the intensity of the C(002) peak of Examples 2, 3 increases and becomes more sharp as the loading of potassium ferrate increases; the patterns of Comparative Examples 1 and 2, which were heat-treated at the same temperature but without using iron catalyst, exhibit a broad C(002) peak shifted to the negative direction, indicating that the samples contain a large amount of disordered carbon or amorphous phase; the degree of graphitization of Comparative Example 2 is reduced by 25.56% compared with Comparative Example 1, indicating that steam activation has a certain destructive effect on the graphite structure of carbon materials; when iron is added, significant changes in peak position and morphology are observed even in Example 1 with a loading of only 0.05 mg / L, which reveals the key catalytic role of iron in the evolution of carbon structure, i.e., the addition of potassium ferrate for catalytic graphitization can obtain carbon materials with more ordered structure at the same activation temperature, and effectively prevents the destruction of steam activation to the graphite structure.

[0090] In the process of preparing activated carbon materials by "one-pot method", potassium ferrate plays two key roles. First, it serves as a source of activator, providing potassium hydroxide to react with raw coal to initiate the activation reaction; second, as a compound containing iron, it also acts as a catalyst to promote the graphitization treatment on the surface of the sample. Potassium ferrate, through simultaneous activation and graphitization treatment, enables the carbon material to have a more developed pore structure and a more hydrophobic graphitized surface. The main reactions in this process are the activation reaction of potassium hydroxide and the catalytic reaction of iron series, as shown in equation (1).

[0091] 4K2Fe04+ 10H20→ 8KOH + 4Fe(OH)3+ 3O2(1) In the potassium hydroxide activation process, the initial stage is a solid-solid reaction, which then evolves into a solid-liquid interaction: the potassium-containing compound is reduced to metallic potassium, while the carbon is oxidized to carbon monoxide, carbon dioxide, and carbonates, accompanied by the reaction of other types of intermediate active products. Under the dual action of these physical and chemical processes, the crystal structure of the sample undergoes irreversible changes and eventually forms a rich pore structure with high microporosity. Compared with Comparative Example 2, which uses only steam for activation, the micropore volume of Example 2 is improved.

[0092] The growth mechanism of iron catalyst to produce graphite nanostructures is as follows Figure 7The iron particles exhibit a state similar to melting when the temperature is raised to a certain value during the high-temperature preparation process. Due to random diffusion effect, iron-carbon interaction, interaction between iron nanoparticles, external force such as gravity, or the combined action of multiple factors, the iron particles tend to move on the surface of the carbon matrix. Carburizing has already started when the iron is still in the solid phase. Amorphous carbon is absorbed by the iron metal crystal when the temperature is higher than 560 ℃. When the temperature is higher than the melting point, the carburized iron will melt, and the liquid iron-carbon droplets will wrap the surface of the raw coal. When the carbon in the metal crystal reaches saturation, the graphene layer will nucleate, precipitate and grow on the surface of the metal crystal. The precipitated carbon will form small irregular sheet structures, and the edges of these newly born carbon nanostructures will have a large number of unsaturated dangling bonds. The dangling bonds tend to form new bonds with the carbon matrix to form integrated carbon structures, i.e. to be transformed into graphite crystals through growth and aggregation. Since the graphene is grown at a constant temperature or even under the condition of increasing temperature, the supersaturation nucleation phenomenon caused by cooling can be ruled out. In addition, the thickness of the graphene, i.e. the number of layers, will increase with the increase of the solubility of carbon in the corresponding metal, and the solubility of carbon in iron is high, which will usually produce multi-layer graphene. The diffusion speed of carbon in all transition metals is very fast, so the diffusion can be ruled out as a limitation in this growth process. The metal crystal acts as a diffusion channel to quickly transport carbon atoms to every position on the surface, thereby forming a continuous graphene layer.

[0093] Test Example 5: Atomic force microscope test of the activated carbon material.

[0094] Test sample: activated carbon material prepared in Example 2 and Comparative Examples 1-2.

[0095] Test method: The surface structure and properties of the activated carbon material were analyzed by atomic force microscopy. The X-Y direction scanning range was 90 μm*90 μm typical value, the Z direction scanning range was 10 μm typical value, the X-Y axis of the electrically driven positioning sample table was 180 mm*180 mm visual area, and the average micro-domain and particle diameter were determined by calculating 300 micro-domains or particles in the atomic force microscope image.

[0096] The atomic force microscope of the activated carbon material prepared in the application is shown in Figure 8 , wherein Figure 8 (a) is the atomic force microscope schematic diagram of Comparative Example 1, Figure 8 (b) is the atomic force microscope schematic diagram of Comparative Example 2, Figure 8 (c) is the atomic force microscope schematic diagram of Example 2; and the particle size distribution of the activated carbon material prepared in the application is shown in Figure 9 , wherein Figure 9 (a) is the particle size distribution schematic diagram of Comparative Example 1, Figure 9 (b) is the particle size distribution schematic diagram of Comparative Example 2, Figure 9(c) is a schematic diagram of particle size distribution in Example 2; the average diameter of the activated carbon material prepared by the present invention is shown in Table 3.

[0097] Table 3. X-ray quantitative analysis of activated carbon materials Activated carbon material Average diameter (nm) Example 1 4.62 Example 2 5.40 Example 3 5.56 Example 4 5.71 Example 5 5.75 Example 6 5.82 Example 7 5.88 Comparative Example 1 4.58 Comparative Example 2 2.94 Comparative Example 3 3.05 Comparative Example 4 3.27 Example 1 used a low amount of potassium ferrate, resulting in moderate micropore volume and uniform pore structure. Compared to Example 1, Examples 2-3 increased the amount of potassium ferrate, significantly increasing micropore volume, porosity, and the average diameter of the activated carbon material. Examples 4-5, after modification with tricresyl phosphate and tetraisobutyl titanate during pretreatment, optimized surface hydrophilicity and hydrophobicity, improved particle dispersibility, and further increased the average diameter. Example 6 added ethylaminethiophene, and Example 7 increased the amount of ethylaminethiophene. The addition of ethylaminethiophene enhanced the dispersibility of potassium ferrate and catalyzed graphitization. The activated carbon materials exhibited more uniform and regular pore distribution, resulting in reduced interparticle friction and the largest average diameter in Example 7. Comparative Example 1, lacking activation treatment, suffered from insufficient pore development and dense particle packing. Comparative Example 2, activated only with water vapor, resulted in a coarse pore structure and rough particle surfaces. Comparative Example 3, modified solely with tricresyl phosphate, and Comparative Example 4, modified solely with tetraisobutyl titanate, failed to synergistically catalyze graphitization, leading to insufficient pore development and a smaller average diameter. This demonstrates that tricresyl phosphate or tetraisobutyl titanate work synergistically to effectively enrich the microporous structure of the activated carbon materials.

[0098] Comparative Example 1 mainly consists of spherical microdomains of 2-5 nm, which are composed of graphene sheets. Comparative Example 2, after steam activation, shows a significant reduction in microdomain size, primarily composed of spherical microdomains of 1-4 nm. Compared to Comparative Example 1, its larger 4-10 nm microdomains are significantly reduced, and the average diameter of the microdomains decreases. However, the spherical shape of the microdomain structure remains unchanged, and the distribution is more disordered. This may be because the oxidation reaction of steam preferentially occurs on the outer surface of the carbon particles and microdomains, leading to the vaporization of the outermost layer, thus reducing the microdomain size while maintaining its shape. The microdomains of Example 2, generated using potassium ferrate-assisted steam activation, show a more uniform distribution. The average diameter increased significantly, with microdomains of 4-10 nm showing a substantial increase compared to Comparative Examples 1-2, particularly a 3.87-fold increase compared to Comparative Example 2. This indicates that during graphitization, the microdomain structure of the activated carbon material connected, resulting in larger microdomains with a more ordered arrangement. Before potassium ferrate treatment, the boundaries of the microdomains in the activated carbon material were clear, meaning that the probability of interconnection between microdomains was very low. However, potassium ferrate treatment clearly promotes the merging of individual microdomains in the activated carbon material, thereby generating larger microdomains with more regular orientation. The ability of activated carbon materials to merge their own microdomains into larger and more ordered stacked microdomains will determine their graphitization properties.

[0099] Based on the micro-domain structure model, a development mechanism of pores and graphitization structure in graphitized microporous carbon was proposed at the nanostructure level, such as... Figure 10 As shown. Under steam activation conditions, the microdomains located on the periphery of the particles are completely vaporized, leading to a reduction in particle size. The remaining microdomains located in the core of the particles are likely to be activated unevenly, meaning that only a portion of the remaining microdomains form micropores, while the central region remains unchanged. Simultaneously, due to the reduction in size of the partially activated microdomains, the distance between microdomains increases, which helps to generate mesopores in highly activated carbon materials. The activation process inside the microdomains is also enhanced through the external exposure of these mesopores to the microdomains. Therefore, the carbon material produced by steam activation has a wide pore size distribution, including mesopores, inter-microdomain pores generated by the reduction in microdomain diameter; relatively large micropores distributed on the outermost microdomains; and small micropores newly formed in the core microdomains. When potassium ferrate is added to assist steam activation, the characteristics of Example 2 reveal the influence of potassium-containing and iron-containing compounds on its structural development. On the one hand, potassium-containing compounds can promote the efficient and uniform formation of pores in the microdomains without changing the microdomain size. In particular, the intercalation reaction after the potassium atoms vaporize accelerates the activation efficiency and generates more micropores. On the other hand, the melting, carburizing, and graphene precipitation of the iron catalyst on the surface of carbon materials can lead to the interconnection or merging of some microdomains, resulting in larger and more uniform domains. The 5-10 nm microdomains increased by 63.33% compared to Comparative Example 1 and by 661.37% compared to Comparative Example 2. That is, the addition of potassium ferrate largely suppressed the reduction in microdomain size caused by water vapor activation.

[0100] Experimental Example 6: Long-term stability test of activated carbon materials.

[0101] Test samples: Activated carbon materials prepared in each embodiment and comparative example.

[0102] Test method: The initial adsorption capacity q0 of 2-methylisoborneol of activated carbon material was tested. Under the condition of 25℃, the activated carbon material was placed in 500mL of 1μg / L 2-methylisoborneol solution and the adsorption experiment was carried out for 300h. The adsorption capacity q1 of 2-methylisoborneol of activated carbon material after 300h was tested. The stability was calculated according to the formula K= (q1 / q0)×100%.

[0103] The long-term stability test results of the activated carbon material prepared by this invention are shown in Table 4.

[0104] Table 4. Long-term stability test of activated carbon materials Activated carbon material Stability (%) Example 1 90.2 Example 2 92.5 Example 3 92.8 Example 4 92.3 Example 5 92.7 Example 6 94.1 Example 7 94.5 Comparative Example 1 62.1 Comparative Example 2 75.3 Comparative Example 3 70.5 Comparative Example 4 72.8 Example 1 uses micro-melting of high-iron potassium to assist steam activation, forming a stable graphitized carbon skeleton, and the surface residual iron-carbon composite enhances the oxidation resistance, and can maintain high stability under long-time adsorption; compared with Example 1, Examples 2 and 3 increase the amount of high-iron potassium, and the stability is further improved; Examples 4-5 add o-phosphorylated trimethylphenol ester and titanium acid tetraisobutyl ester during pretreatment, and after modification, the surface hydrophilicity and hydrophobicity are optimized, the particle dispersibility is improved, the microporous structure effectively protects the adsorption sites, and the stability is effectively improved; Example 6 adds ethylamine thiophene, and Example 7 increases the amount of ethylamine thiophene; the sulfur doping and dispersion of ethylamine thiophene make the high-iron potassium uniformly distributed, form a more stable iron-carbon composite, and at the same time, the microporous structure protects the adsorption sites from oxidation, and the stability is the highest; Comparative Example 1 is not activated, has low porosity, and the disordered carbon on the surface is easy to be oxidized, and the adsorption sites are quickly deactivated; Comparative Example 2 forms mesopores by steam activation, which exposes more active sites, but the graphitization degree is low, and the structural stability is insufficient; Comparative Example 3 uses o-phosphorylated trimethylphenol ester modification alone, and Comparative Example 4 uses titanium acid tetraisobutyl ester modification alone, and cannot form a stable composite structure, the pore distribution is uneven, and the adsorption capacity decays quickly.

[0105] The above-described embodiments and / or implementations are merely used to illustrate the preferred embodiments and / or implementations of the present application, and are not intended to limit the embodiments of the present application in any form. Any person skilled in the art can make some changes or modifications to other equivalent embodiments without departing from the scope of the technical means disclosed in the present application, and such changes or modifications should be considered as substantially the same technology or embodiments of the present application.

[0106] The principles and implementations of the present application are described by using specific examples in this paper, and the above example description is only used to help understand the method and core idea of the present application. The above description is only the preferred embodiments of the present application, and it should be pointed out that due to the limitation of language expression, there are infinite specific structures, and for ordinary skilled persons in the technical field, some improvements, refinements or changes can be made without departing from the principles of the present application, and the above technical features can be combined in an appropriate manner; these improvements, refinements, changes or combinations, or the direct application of the inventive concept and technical scheme to other occasions without improvement, should be considered as the protection scope of the present application.

Claims

1. A microporous, highly graphitized deodorizing powder carbon, comprising a graphitized framework carbon, wherein iron and potassium elements are distributed on the surface of the microporous, highly graphitized deodorizing powder carbon, wherein, The graphitization degree of the graphitized framework carbon is 20%-50%. The micropore volume of the highly graphitized, microporous deodorizing carbon powder is 0.25-0.5 cm³. 3 / g, The iron element accounts for 0.1%-0.5% of the mass percentage in the microporous, highly graphitized deodorizing carbon powder.

2. The microporous, highly graphitized deodorizing powder carbon according to claim 1, characterized in that, The highly graphitized, microporous deodorizing powder carbon has spherical microdomains with an average diameter of 4-6 nm. The spherical microdomain includes small-sized microdomains and large-sized microdomains. The diameter of the small-sized microdomains is 1-4 nm, and the diameter of the large-sized microdomains is 4-10 nm. The proportion of large-sized microdomains in the spherical microdomains is 60-90%.

3. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 1, comprising the following preparation steps: Pretreated raw coal is obtained by deashing and modifying the raw coal. Pretreated raw coal is impregnated in potassium ferrate solution, and then carbonized and activated to obtain microporous, highly graphitized deodorizing powder carbon.

4. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 3, characterized in that, The mass of the potassium ferrate solution is measured by the mass of potassium ferrate therein, and the mass ratio of potassium ferrate to pretreated raw coal is 1-100 mg: 20-2000 g.

5. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 3, characterized in that, The solution used for deashing includes hydrochloric acid solution and hydrofluoric acid solution, wherein the volume ratio of hydrofluoric acid solution to hydrochloric acid solution is 0.2-2:0.2-2.

6. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 3, characterized in that, The reagents used in the modification include trimethylol phosphate and tetraisobutyl titanate.

7. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 6, characterized in that, The mass ratio of tetraisobutyl titanate to tricresyl phosphate is 2-20:3-30.

8. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 3, characterized in that, The carbonization temperature is 550-650℃.

9. The method for preparing a microporous, highly graphitized deodorizing powder carbon according to claim 3, characterized in that, The activation is carried out by steam activation at a temperature of 800-900℃ and a steam flow rate of 0.4-0.6 mL / min.

10. The use of the microporous, highly graphitized deodorizing powder carbon according to claims 1-2 in adsorbing odor substances, wherein the odor substances include 2-methylisoborneol and geosmin.

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