CN111804279A - Preparation method of carbon material for dye wastewater, product and application thereof - Google Patents
Preparation method of carbon material for dye wastewater, product and application thereof Download PDFInfo
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a preparation method of a carbon material for dye wastewater, and a product and application thereof. According to the invention, an iron source, a silicon source, polyvinyl alcohol and the like are uniformly mixed, a hydrothermal reaction is carried out to obtain a composite material containing ferroferric oxide and silicon oxide, then the composite material is mixed with animal manure, SBA-15 and water to be loaded on the surface of the composite material of the ferroferric oxide and the silicon oxide, an intermediate product is obtained through carbonization, then nitric acid modification is carried out to oxidize only the surface of a carbon material, then the silicon oxide and the SBA-15 are dissolved out through sodium hydroxide etching, and a porous structure with a core-shell structure is further obtained.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a preparation method of a carbon material for dye wastewater, and a product and application thereof.
Background
The development of the dye industry brings about a great problem of environmental pollution, the problems of high chroma, difficult degradation, large toxin and the like of colored waste water generated in printing and dyeing waste water bring great harm to water organisms, and the colored waste water indirectly causes harm to human bodies through food chain enrichment. Therefore, the treatment of the waste water is problematic to be forced on the brow apex.
At present, a plurality of methods for treating dye wastewater are available, such as membrane separation, photocatalytic degradation, an ozone oxidation method, an adsorption method and the like, and the adsorption method has the advantages of high efficiency, high speed, strong adaptability, easy operation and the like for removing pollutants in water, so that the method is widely applied to the treatment of dye wastewater. In the adsorption process for treating wastewater, the main factor influencing the adsorption efficiency is the selection of the adsorbent.
The adsorption effect of 100g/L Congo red simulated printing and dyeing wastewater is the best by using NaOH-modified bamboo leaf powder (MBL) as an adsorbent in Yangxing and the like and adopting a static adsorption method under the conditions that the addition amount of the MBL is 2.0g/L, the adsorption time is 120min, and the pH value is 7.0, and the removal rate can reach 96.29%; the Chinese parasol tree bark is used as a raw material of Weixinlai and the like, and the Chinese parasol tree bark activated carbon is prepared by activating with zinc chloride, and a large amount of mesoporous structures exist in the Chinese parasol tree bark activated carbon, so that the pore structure is developed; the adsorption effect of the activated carbon of the phoenix tree bark on Congo red in sewage can be improved by increasing the using amount of the activated carbon, and the removal rate of the Congo red can reach 98.2% under the conditions of room temperature, the adding amount of 3.0g/L, the adsorption time of 120min and the oscillation speed of 60 r/min. Although the above carbon material achieves excellent adsorption performance, it is inferior in recovery ratio and low in recycling rate. The adsorption capacity is yet to be further improved.
Based on the above situation, there is an urgent need to develop a low-cost carbon material having a large specific surface area, excellent adsorption performance, excellent separation ability, and a high recycling rate, and still remains a technical problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a carbon material for dye wastewater, a product and an application thereof aiming at the defects in the prior art. The invention mixes iron source, silicon source, polyvinyl alcohol, etc. uniformly, then carries on hydrothermal reaction to obtain composite material containing ferriferrous oxide and silicon oxide, then mixes it withAnimal waste, SBA-15 and water are mixed, the mixture of the animal waste and the SBA-15 is loaded on the surface of a composite material of ferroferric oxide and silicon oxide, an intermediate product is obtained through carbonization, then nitric acid modification is carried out, only the surface of a carbon material is oxidized, functional groups on the surface are improved, then the silicon oxide and the SBA-15 are dissolved out through etching of sodium hydroxide, and then the carbon material with a core-shell structure is obtained, and Fe is effectively avoided3O4The carbon material prepared by the method has excellent specific surface area and active groups, has excellent adsorption capacity on dyes in wastewater, and is an ideal material for removing dye wastewater.
The invention adopts the following technical scheme:
a preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding soluble ferric ion salt into 100-120 mL of glycol solution to prepare 0.1-0.4 mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1000-2000, anhydrous sodium carbonate and 20-25 mL of ethyl silicate TEOS, stirring for 3-5 h, uniformly dispersing, transferring into a polytetrafluoroethylene reaction kettle, and reacting for 20-30 h at the temperature of 200-230 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 90-110 ℃ for 8-12 hours to obtain a product A;
(2) ultrasonically dispersing and mixing the animal waste, SBA-15 and deionized water to obtain a dispersion liquid, then adding the product A into the dispersion liquid, continuously stirring for 4-6 h, and then drying for 10-12 h at 90-110 ℃ to obtain a product B;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein inert gas is used as protective gas, and the temperature is 3-5 ℃ per minute-1After the temperature rise rate is heated to 450-550 ℃, pre-calcining is carried out for 3-5 h, and then the temperature rise rate is 7-9 ℃ per minute-1Heating to 800-900 ℃, preserving heat for 3-5 h, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 3-6 mol/L nitric acid solution with the solid-liquid ratio of (1-4) g (10-40) ml, uniformly stirring for 4-6 hours by using a stirrer, standing for 6-10 hours, repeatedly washing to be neutral by using distilled water, and drying to obtain a product D;
(5) and transferring the product D into a NaOH solution, heating to 80-90 ℃, reacting for 14-20 h, washing with water to be neutral, separating, and drying to obtain the carbon material.
Preferably, in step (1), the ferric ion salt is one or more of ferric trichloride, ferric sulfate, ferric nitrate and ferric acetate.
Preferably, in the step (1), the concentration of the polyvinyl alcohol is 0.01-0.1 mol/L, and the added anhydrous sodium carbonate is 0.09-0.11 g/mL.
Preferably, in the step (2), the ratio of the animal wastes to the molecular sieve and the deionized water is 20-24 g: 1g: 38-42 mL; the animal manure is one or more of chicken manure, pig manure, duck manure and cattle manure.
Preferably, in the step (2), the aperture of the SBA-15 is 8-14 nm; the specific surface area can be 900-1100m2(ii)/g; the pore volume is 3-6 cm3(ii)/g; the adsorption capacity may be 45-65 mg/g.
Preferably, in the step (3), the inert gas is He or Ar.
Preferably, in the step (4), the drying is carried out at 90-110 ℃ for 10-12 h.
Preferably, in the step (5), the molar concentration of the NaOH solution is 0.9-2.1 mol/L; the drying is carried out for 4-6 h at the temperature of 25-75 ℃.
According to another technical scheme, the carbon material for dye wastewater prepared by the preparation method is a carbon material with porous ferroferric oxide as a core and mesoporous carbon as a shell, and the specific surface area of the carbon material for wastewater treatment is 1923.5-2126.4 m2/g。
According to another technical scheme, based on the application of the carbon material for dye wastewater, the carbon material is used for treating dye wastewater, and specifically, 0.05-0.2 g of the carbon material is weighed and placed in a 250ml conical flask, 90-110 ml of a 100-120 mg/L solution of methylene blue, methyl orange or rhodamine B is added, and the mixture is stirred at normal temperature for 30-50 min.
The preparation method, the product and the application of the carbon material for dye wastewater provided by the invention have the following technical effects:
(1) the carbon material prepared by adopting the animal wastes as the carbon source not only enriches the raw materials, but also has low price, and simultaneously can change waste into valuables.
(2) The iron source, the silicon source and the like are directly mixed, then the composite material containing ferroferric oxide and silicon oxide is obtained through hydrothermal preparation, the carbon material is synthesized on the surface of the composite material, then nitric acid modification treatment is carried out, and sodium hydroxide treatment is carried out, so that the dissolution of iron can be effectively avoided, the active groups on the surface of the carbon material can be improved through nitric acid modification, more adsorption sites are provided, and the existence of the ferroferric oxide can obviously improve magnetic separation and improve the reutilization of the carbon material.
(3) The composite material of ferroferric oxide and silicon oxide is treated by sodium hydroxide, and then the silicon oxide is dissolved out to obtain the ferroferric oxide with a porous structure, and the ferroferric oxide also has adsorption capacity due to the existence of the pores, and meanwhile, the adsorption effect is further improved due to the synergistic effect of the ferroferric oxide and the silicon oxide when the ferroferric oxide is compounded with a carbon material.
In conclusion, the carbon material for dye wastewater prepared by the invention has the advantages of large surface area, rich pore structure and good adsorption capacity for dye in dye wastewater, and is an ideal material for wastewater treatment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding ferric chloride into 110mL of glycol solution to prepare 0.25mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1700, anhydrous sodium carbonate and 24mL of ethyl silicate TEOS, stirring for 4 hours, uniformly dispersing, then transferring to a polytetrafluoroethylene reaction kettle, and reacting for 25 hours at 220 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 100 ℃ for 10 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.05mol/L, and the added anhydrous sodium carbonate is 0.1 g/mL;
(2) ultrasonically dispersing and mixing pig manure, SBA-15 and deionized water to obtain a dispersion liquid, adding a product A into the dispersion liquid, continuously stirring for 4-6 hours, and drying for 10-12 hours at 90-110 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 22g: 1g: 40 mL; the aperture of the SBA-15 is 10 nm; the specific surface area may be 1050m2(ii)/g; pore volume is 5cm3(ii)/g; the adsorption capacity may be 60 mg/g;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein He is used as protective gas, and the temperature is 4 ℃ min-1After heating to 500 ℃, pre-calcining for 4h, and then calcining at 8 ℃ for min-1Heating to 850 ℃, preserving heat for 4 hours, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 4.5mol/L nitric acid solution with the solid-to-liquid ratio of 2.5g:25ml, uniformly stirring for 5 hours by using a stirrer, standing for 8 hours, repeatedly washing to be neutral by using distilled water, and drying for 11 hours at 100 ℃ to obtain a product D;
(5) transferring the product D into 100mL of 1.5mol/L NaOH solution, heating to 85 ℃ for reacting for 18h, washing with water to be neutral, separating, and drying at 40 ℃ for 5h to obtain the carbon material.
Example 2
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding ferric nitrate into 120mL of glycol solution to prepare 0.4mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with molecular weight of 2000, anhydrous sodium carbonate and 25mL of ethyl silicate TEOS, stirring for 5 hours, uniformly dispersing, then transferring into a polytetrafluoroethylene reaction kettle, and reacting for 20 hours at 230 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 110 ℃ for 8 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.1mol/L, and the added anhydrous sodium carbonate is 0.11 g/mL;
(2) ultrasonically dispersing and mixing chicken manure, SBA-15 and deionized water to obtain a dispersion liquid, then adding a product A into the dispersion liquid, continuously stirring for 6 hours, and then drying for 12 hours at 110 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 24g: 1g: 42 mL; the aperture of the SBA-15 is 14 nm; the specific surface area may be 1100m2(ii)/g; the pore volume is 6cm3(ii)/g; the adsorption capacity may be 65 mg/g;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein Ar is used as protective gas, and the temperature is 5 ℃ min-1After heating to 550 ℃, pre-calcining for 3h, and then at 9 ℃ for min-1Heating to 900 ℃, preserving heat for 3 hours, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 6mol/L nitric acid solution with a solid-to-liquid ratio of 4g:10ml, uniformly stirring for 6 hours by using a stirrer, standing for 6 hours, repeatedly washing to be neutral by using distilled water, and drying at 110 ℃ for 10 hours to obtain a product D;
(5) transferring the product D into 100mL of 2.1mol/L NaOH solution, heating to 90 ℃ for reaction for 14h, washing with water to be neutral, separating, and drying at 75 ℃ for 4h to obtain the carbon material.
Example 3
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding iron acetate into 100mL of glycol solution to prepare 0.1mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1000, anhydrous sodium carbonate and 20mL of ethyl silicate TEOS, stirring for 5 hours, uniformly dispersing, then transferring into a polytetrafluoroethylene reaction kettle, and reacting for 30 hours at the temperature of 200 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 90 ℃ for 12 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.01mol/L, and the added anhydrous sodium carbonate is 0.09 g/mL;
(2) ultrasonically dispersing and mixing cow dung, SBA-15 and deionized water to obtain a dispersion liquid, then adding a product A into the dispersion liquid, continuously stirring for 4 hours, and then drying for 12 hours at 90 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 20g: 1g: 38 mL; the aperture of the SBA-15 is 8 nm; the specific surface area may be 900m2(ii)/g; pore volume is 3cm3(ii)/g; the adsorption capacity may be 45 mg/g;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein He is used as protective gas, and the temperature is 3 ℃ min-1After heating to 450 ℃ at the temperature rise rate, pre-calcining for 5 hours, and then carrying out calcination at 7 ℃ for min-1Heating to 800 ℃, preserving heat for 5 hours, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 3mol/L nitric acid solution with the solid-to-liquid ratio of 1g to 10ml, uniformly stirring for 4 hours by using a stirrer, standing for 6 hours, repeatedly washing to be neutral by using distilled water, and drying to obtain a product D; the drying is carried out for 12 hours at the temperature of 90 ℃;
(5) transferring the product D into 100mL of 0.9mol/L NaOH solution, heating to 80 ℃ for reaction for 20h, washing with water to be neutral, separating, and drying at 25 ℃ for 6h to obtain the carbon material.
Comparative example 1
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding ferric chloride into 110mL of glycol solution to prepare 0.25mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1700 and anhydrous sodium carbonate, stirring for 4 hours, uniformly dispersing, then transferring to a polytetrafluoroethylene reaction kettle, and reacting for 25 hours at 220 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 100 ℃ for 10 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.05mol/L, and the added anhydrous sodium carbonate is 0.1 g/mL;
(2) ultrasonically dispersing and mixing pig manure, SBA-15 and deionized water to obtain a dispersion liquid, adding a product A into the dispersion liquid, continuously stirring for 4-6 hours, and drying for 10-12 hours at 90-110 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 22g: 1g: 40 mL; the aperture of the SBA-15 is 10 nm; the specific surface area may be 1050m2(ii)/g; pore volume is 5cm3(ii)/g; the adsorption capacity may be 60 mg/g;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein He is used as protective gas, and the temperature is 4 ℃ min-1After heating to 500 ℃, pre-calcining for 4h, and then calcining at 8 ℃ for min-1Heating to 850 ℃, preserving heat for 4 hours, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 4.5mol/L nitric acid solution with the solid-to-liquid ratio of 2.5g:25ml, uniformly stirring for 5 hours by using a stirrer, standing for 8 hours, repeatedly washing to be neutral by using distilled water, and drying for 11 hours at 100 ℃ to obtain a product D;
(5) transferring the product D into 100mL of 1.5mol/L NaOH solution, heating to 85 ℃ for reacting for 18h, washing with water to be neutral, separating, and drying at 40 ℃ for 5h to obtain the carbon material.
Comparative example 2
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) taking 110mL of ethylene glycol solution, adding a proper amount of polyvinyl alcohol with molecular weight of 1700, anhydrous sodium carbonate and 24mL of ethyl silicate TEOS, stirring for 4 hours, uniformly dispersing, transferring to a polytetrafluoroethylene reaction kettle, and reacting for 25 hours at 220 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 100 ℃ for 10 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.05mol/L, and the added anhydrous sodium carbonate is 0.1 g/mL;
(2) ultrasonically dispersing and mixing pig manure, SBA-15 and deionized water to obtain a dispersion liquid, adding a product A into the dispersion liquid, continuously stirring for 4-6 hours, and drying for 10-12 hours at 90-110 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 22g: 1g: 40 mL; the aperture of the SBA-15 is 10 nm; the specific surface area may be 1050m2(ii)/g; pore volume is 5cm3(ii)/g; the adsorption capacity may be 60 mg/g;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein He is used as protective gas, and the temperature is 4 ℃ min-1After heating to 500 ℃, pre-calcining for 4h, and then calcining at 8 ℃ for min-1Heating to 850 ℃, preserving heat for 4 hours, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 4.5mol/L nitric acid solution with the solid-to-liquid ratio of 2.5g:25ml, uniformly stirring for 5 hours by using a stirrer, standing for 8 hours, repeatedly washing to be neutral by using distilled water, and drying for 11 hours at 100 ℃ to obtain a product D;
(5) transferring the product D into 100mL of 1.5mol/L NaOH solution, heating to 85 ℃ for reacting for 18h, washing with water to be neutral, separating, and drying at 40 ℃ for 5h to obtain the carbon material.
Comparative example 3
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) ultrasonically dispersing and mixing pig manure, SBA-15 and deionized water to obtain a dispersion liquid, adding a product A into the dispersion liquid, continuously stirring for 4-6 hours, and drying for 10-12 hours at 90-110 ℃ to obtain a product B; the ratio of the animal waste to the molecular sieve and the deionized water is 22g: 1g: 40 mL; the aperture of the SBA-15 is 10 nm; the specific surface area may be 1050m2(ii)/g; pore volume is 5cm3(ii)/g; the adsorption capacity may be 60 mg/g;
(2) then placing the product B prepared in the step (1) in a quartz boat, wherein He is used as protective gas, and the temperature is 4 ℃ min-1Is disclosedHeating to 500 deg.C at a temperature rate, pre-calcining for 4 hr, and calcining at 8 deg.C/min-1Heating to 850 ℃, preserving heat for 4 hours, and then cooling to room temperature to obtain a product C;
(3) adding the product C into 4.5mol/L nitric acid solution with the solid-to-liquid ratio of 2.5g:25ml, uniformly stirring for 5 hours by using a stirrer, standing for 8 hours, repeatedly washing to be neutral by using distilled water, and drying for 11 hours at 100 ℃ to obtain a product D;
(4) transferring the product D into 100mL of 1.5mol/L NaOH solution, heating to 85 ℃ for reacting for 18h, washing with water to be neutral, separating, and drying at 40 ℃ for 5h to obtain the carbon material.
Comparative example 4
A preparation method of a carbon material for dye wastewater comprises the following steps:
(1) adding ferric chloride into 110mL of glycol solution to prepare 0.25mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1700, anhydrous sodium carbonate and 24mL of ethyl silicate TEOS, stirring for 4 hours, uniformly dispersing, then transferring to a polytetrafluoroethylene reaction kettle, and reacting for 25 hours at 220 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 100 ℃ for 10 hours to obtain a product A; the concentration of the polyvinyl alcohol is 0.05mol/L, and the added anhydrous sodium carbonate is 0.1 g/mL;
(2) transferring the product A into 100mL of 1.5mol/L NaOH solution, heating to 85 ℃ for reacting for 18h, washing with water to be neutral, separating, and drying at 40 ℃ for 5h to obtain the carbon material.
The carbon materials of examples 1 to 3 and comparative examples 1 to 4 were analyzed for specific surface area using a specific surface area analyzer (Autosorb Iq3, Congta, USA). Specific results are shown in table 1:
TABLE 1 specific surface areas of examples 1-3 and comparative examples 1-4
As can be seen from table 1, the carbon material of the core-shell structure prepared by the preparation method of the present application has a high specific surface area.
The carbon materials of examples 1 to 3 and comparative examples 1 to 4 were used for the treatment of dye wastewater. The specific method comprises the following steps:
specifically, 0.1g of the carbon material of example 1 was weighed and placed in a 250mL Erlenmeyer flask, and 100mL of a 110mg/L methine blue solution was added thereto and stirred at room temperature for 40 min. The adsorption of methyl orange and rhodamine B were tested using the same test conditions.
Examples 2-3 and comparative examples 1-4 were tested for methine blue, adsorbed methyl orange and rhodamine B using the same conditions as in example 1. The specific results are shown in Table 2.
TABLE 2
As can be seen from the comparison between example 1 and comparative examples 1 to 4, the carbon material of the present invention has excellent adsorption performance, has a good effect of removing organic dyes from wastewater, and is an ideal material for wastewater treatment.
After repeating the carbon material of example 14 times, the regenerated carbon material was treated to adsorb the dye wastewater under the same test conditions for the 5 th time, and the removal rates of methylene blue, adsorbed methyl orange and rhodamine B were 94.3%, 94.5% and 93.8%, respectively. Therefore, the carbon material has good repeatability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon material for dye wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) adding soluble ferric ion salt into 100-120 mL of glycol solution to prepare 0.1-0.4 mol/L solution, simultaneously adding a proper amount of polyvinyl alcohol with the molecular weight of 1000-2000, anhydrous sodium carbonate and 20-25 mL of ethyl silicate TEOS, stirring for 3-5 h, uniformly dispersing, transferring into a polytetrafluoroethylene reaction kettle, and reacting for 20-30 h at the temperature of 200-230 ℃; cooling to room temperature, performing magnetic separation, washing the obtained product with ethanol and deionized water, and performing vacuum drying at 90-110 ℃ for 8-12 hours to obtain a product A;
(2) ultrasonically dispersing and mixing the animal waste, SBA-15 and deionized water to obtain a dispersion liquid, then adding the product A into the dispersion liquid, continuously stirring for 4-6 h, and then drying for 10-12 h at 90-110 ℃ to obtain a product B;
(3) then placing the product B prepared in the step (2) in a quartz boat, wherein inert gas is used as protective gas, and the temperature is 3-5 ℃ per minute-1After the temperature rise rate is heated to 450-550 ℃, pre-calcining is carried out for 3-5 h, and then the temperature rise rate is 7-9 ℃ per minute-1Heating to 800-900 ℃, preserving heat for 3-5 h, and then cooling to room temperature to obtain a product C;
(4) adding the product C into 3-6 mol/L nitric acid solution with the solid-liquid ratio of (1-4) g (10-40) ml, uniformly stirring for 4-6 hours by using a stirrer, standing for 6-10 hours, repeatedly washing to be neutral by using distilled water, and drying to obtain a product D;
(5) and transferring the product D into a NaOH solution, heating to 80-90 ℃, reacting for 14-20 h, washing with water to be neutral, separating, and drying to obtain the carbon material.
2. The method of claim 1, wherein: in the step (1), the ferric ion salt is one or more of ferric trichloride, ferric sulfate, ferric nitrate and ferric acetate.
3. The method of claim 1, wherein: in the step (1), the concentration of the polyvinyl alcohol is 0.01-0.1 mol/L, and the added anhydrous sodium carbonate is 0.09-0.11 g/mL.
4. The method of claim 1, wherein: in the step (2), the ratio of the animal wastes to the molecular sieve and the deionized water is 20-24 g: 1g: 38-42 mL; the animal manure is one or more of chicken manure, pig manure, duck manure and cattle manure.
5. The method of claim 1, wherein: in the step (2), the aperture of the SBA-15 is 8-14 nm; the specific surface area can be 900-1100m2(ii)/g; the pore volume is 3-6 cm3(ii)/g; the adsorption capacity may be 45-65 mg/g.
6. The method of claim 1, wherein: in the step (3), the inert gas is He or Ar.
7. The method of claim 1, wherein: in the step (4), the drying is carried out at 90-110 ℃ for 10-12 h.
8. The method of claim 1, wherein: in the step (5), the molar concentration of the NaOH solution is 0.9-2.1 mol/L; the drying is carried out for 4-6 h at the temperature of 25-75 ℃.
9. A carbon material for dye wastewater produced by the production method according to any one of claims 1 to 8, characterized in that: the carbon material takes porous ferroferric oxide as a core and mesoporous carbon as a shell, and the specific surface area of the carbon material for wastewater treatment is 1923.5-2126.4 m2/g。
10. The use of the carbon material for dye wastewater according to claim 9, wherein: the carbon material is used for treating dye wastewater, and specifically, 0.05-0.2 g of the carbon material is weighed and placed in a 250ml conical flask, 90-110 ml of a solution of 100-120 mg/L of methylene blue, methyl orange or rhodamine B is added, and stirring is carried out for 30-50 min at normal temperature.
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