CN115970648A - Carbon material for sewage treatment and preparation method thereof - Google Patents
Carbon material for sewage treatment and preparation method thereof Download PDFInfo
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- CN115970648A CN115970648A CN202310258103.7A CN202310258103A CN115970648A CN 115970648 A CN115970648 A CN 115970648A CN 202310258103 A CN202310258103 A CN 202310258103A CN 115970648 A CN115970648 A CN 115970648A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The invention provides a carbon material for sewage treatment and a preparation method thereof, belonging to the field of sewage treatment. The preparation method of the carbon material for sewage treatment comprises the following steps: modifying carbon fibers, preparing materials, preparing a first component, preparing a second component and molding. The carbon material for sewage treatment of the invention realizes good sewage treatment performance for both acidic sewage and alkaline sewage under the condition of low addition amount; and after repeated regeneration and reuse, the sewage treatment performance can be kept, the loss of active ingredients is less, the performance attenuation is reduced, and the long-term service performance is good.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a carbon material for sewage treatment and a preparation method thereof.
Background
Water is an important resource in the life process of human beings, and a large amount of water resources are consumed in the daily production and life processes. With the development of modern industry, deterioration of environment, and excessive use of water resources by human beings, we are facing the crisis of shortage of water resources. Under the circumstances, attention needs to be paid to treatment of industrial sewage, and recycling of the industrial sewage is enhanced on the basis of saving water resources and reducing waste. The method is also an important measure for relieving the pressure of water resources and ensuring sustainable development.
The sewage treatment process in the prior art mainly comprises the following aspects: membrane separation, carbon material adsorption, advanced oxidation, and the like. In the case of the membrane separation method, because the components in the industrial sewage are complex, the membrane pollution problem is generated in the process of sewage treatment by adopting the membrane separation method, and the membrane separation efficiency is low; although a certain membrane separation performance can be recovered by a backwashing technology, in general, the membrane separation method is suitable for industrial sewage with complex components, and still has the problems of poor membrane separation stability, low membrane separation efficiency and high comprehensive sewage treatment cost.
Carbon materials have various properties and forms, and generally consist of more than 85% of carbon, and are the most widely used sewage treatment adsorbing materials in the prior art because of the developed surface microporous structure, the large specific surface area and the good biocompatibility. Conventional carbon materials include activated carbon, charcoal, graphite, carbon fiber, etc., and water and ions in industrial wastewater are overlapped after entering the pores of the carbon material. Therefore, the proper microporous structure of the carbon material is beneficial to the diffusion of adsorbate into micropores, so that the adsorption effect is more stable and effective. The carbon material adsorption method is to utilize the characteristics of the carbon material to adsorb and remove suspended matters, heavy metals and other macromolecular pollutants in industrial sewage through adsorption, and can also effectively promote the formation of activated sludge in water and degrade organic matters in the sewage, thereby achieving the effect of purifying water quality.
The advanced oxidation method comprises photocatalytic oxidation, wet catalytic oxidation and the like, and has obvious treatment effect on chemical sewage. Among them, photocatalytic oxidation is generally performed using a photocatalyst. The photocatalyst has the advantages of biological and chemical inertness, light resistance, chemical corrosion resistance and the like, and is widely applied to the fields of sewage treatment, atmospheric pollutant treatment, microbial degradation and the like at present. When used as a photocatalyst, the photocatalyst has the advantages of high catalytic activity, good selectivity, mild reaction conditions, no corrosion to equipment, small secondary pollution and the like.
The inventor finds that the existing carbon material for sewage treatment needs a larger addition amount to realize an ideal sewage treatment effect in the sewage treatment process, the treatment performance of the carbon material for acidic sewage is inferior to that of alkaline washing sewage, the sewage treatment performance is unstable, and the adaptability needs to be further improved; in addition, after the carbon material after sewage treatment is subjected to regeneration treatment by the conventional regeneration method and recycled for 2-3 times, the sewage treatment efficiency of the carbon material is reduced to be below 80% of the original performance, and the carbon material is poor in long-term use performance. Furthermore, the inventor also finds that the carbon material has the problems of pulverization, loss of active ingredients and the like after repeated regeneration and reuse due to the influence of complex sewage ingredients and sewage treatment process conditions in the sewage treatment process by adopting the carbon material, so that the sewage treatment performance of the carbon material is further reduced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the carbon material for sewage treatment and the preparation method thereof, and in the sewage treatment process, under the condition of low addition amount of the carbon material, the carbon material can realize ideal sewage treatment performance aiming at acidic sewage and alkaline sewage; and after repeated regeneration and reuse, the sewage treatment device can still keep good sewage treatment performance and has good long-term use performance. Meanwhile, the problems of possible pulverization and active ingredient loss after the carbon material is regenerated and recycled for multiple times can be effectively avoided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon material for sewage treatment comprises the following steps: modifying carbon fibers, preparing materials, preparing a first component, preparing a second component and forming.
The carbon fiber modification is carried out by putting polyacrylonitrile-based carbon fiber powder into nitric acid solution with volume of 8-10 times, heating to 35-45 ℃ under stirring, carrying out heat preservation and reflux for 3-5h, filtering, and washing with sufficient deionized water to neutrality; and (2) after the heat preservation and drying are carried out for 6-8h at the temperature of 110-130 ℃, the mixture is put into the first modified liquid with the volume of 6-8 times, the temperature is raised to 40-50 ℃, the mixture is filtered out after ultrasonic dispersion is carried out for 1-2h, the mixture is washed for 2-3 times by using ethanol with the volume of 8-10 times, then the mixture is washed to be neutral by using sufficient deionized water, and the heat preservation and drying are carried out for 8-10h at the temperature of 75-85 ℃ so as to obtain the modified carbon fiber.
In the carbon fiber modification, the mesh number of polyacrylonitrile-based carbon fiber powder is 500-600 meshes;
the concentration of the nitric acid solution is 8-12wt%.
The ultrasonic power of ultrasonic dispersion is 800-1200W, and the ultrasonic frequency is 30-35kHz.
The first modified solution is prepared by the following method, the silane coupling agent KH-570 is put into an ethanol solution, and after the silane coupling agent KH-570 is uniformly mixed, acetic acid is adopted to adjust the pH value to 4-5, so that the first modified solution is prepared.
In the first modified solution, the ratio of the silane coupling agent KH-570 to the ethanol solution in parts by weight is 5-8; the concentration of the ethanol solution is 90-95%.
The preparation method comprises the following steps of (1) preparing materials, namely putting modified carbon fibers into deionized water, and uniformly dispersing by ultrasonic to obtain a solution A;
putting ferric chloride hexahydrate, sodium acetate trihydrate and cobalt acetate tetrahydrate into deionized water, and stirring until the ferric chloride, the sodium acetate trihydrate and the cobalt acetate tetrahydrate are completely dissolved to obtain solution B;
adding L-cysteine into deionized water, and stirring until the L-cysteine is completely dissolved to obtain solution C;
and adding ascorbic acid into deionized water, and stirring until the ascorbic acid is completely dissolved to obtain solution D.
In the preparation of the raw materials, the ratio of the modified carbon fiber in the solution A to the deionized water in parts by weight is 3-5;
the weight ratio of ferric chloride hexahydrate, sodium acetate trihydrate, cobalt acetate tetrahydrate and deionized water in the solution B is 1.3-1.6;
the weight part ratio of the L-cysteine to the deionized water in the solution C is 0.3-0.35;
the weight ratio of the ascorbic acid to the deionized water in the solution D is 0.18-0.2.
The first component is prepared by putting the solution A into the solution B, uniformly mixing, stirring and dropwise adding the solution C at the temperature of 20-30 ℃, and continuously stirring for 3-4 hours after dropwise adding the solution C is finished; then dropwise adding the solution D, and after the dropwise adding of the solution D is finished, ultrasonically dispersing for 20-50min; then transferring the mixture into a hydrothermal reaction kettle with a closed space, controlling the filling degree (the liquid volume accounts for the total volume of the closed space in the hydrothermal reaction kettle) to be 60-70%, heating to 190-200 ℃, carrying out heat preservation for hydrothermal reaction for 8-10h, then naturally cooling to normal temperature, filtering out solids, washing for 2-3 times by using ethanol with the volume of 8-10 times, washing for 2-3 times by using deionized water with the volume of 8-10 times, and then carrying out freeze drying to obtain the first component.
In the preparation of the first component, the dropping rate of the solution C is 3-5mL/min; the dripping speed of the solution D is 0.1-0.2mL/min;
the ultrasonic power of ultrasonic dispersion is 600-700W, and the ultrasonic frequency is 35-40kHz;
the ratio of the parts by weight of the solution A to the solution B to the solution C to the solution D is (1).
The preparation of the second component comprises the steps of putting zeolite powder and a second modification solution into a ball mill, controlling the ball-material ratio to be 5-7; and (3) placing the ball-milled material at 75-85 ℃, preserving heat and drying to constant weight to obtain a second component.
In the second component, the mesh number of the zeolite powder is 200-300 meshes;
the weight ratio of the zeolite powder to the second modification liquid is 1.2-1.5.
The second modified solution is prepared by the following method, the silane coupling agent KH-550 and the silane coupling agent KH-570 are put into an ethanol solution and are uniformly mixed to prepare the second modified solution;
in the second modification liquid, the ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution in parts by weight is 4-5; the concentration of the ethanol solution is 85-95%.
The forming comprises the steps of uniformly mixing the first component, the second component and the titanium dioxide hydrosol, extruding, granulating or performing die pressing for prefabrication, placing in a nitrogen atmosphere environment, heating to 350-400 ℃, and preserving heat for 2-3 hours to obtain a carbon material for sewage treatment;
in the molding, the heating rate is 5-10 ℃/min;
the first component, the second component and the titanium dioxide hydrosol have the weight part ratio of 70-75;
the titanium dioxide hydrosol is anatase type nano titanium dioxide hydrosol, the content of the titanium dioxide is 15-20wt%, and the particle size of the titanium dioxide is 10-20nm.
A carbon material for sewage treatment is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the carbon material for sewage treatment, the polyacrylonitrile-based carbon fiber powder is modified, and the modified carbon fiber is used for preparing the first component; and a specific active ingredient combination and a preparation method are arranged in the first component; setting specific treatment on zeolite powder to prepare a second component; and the first component and the second component are matched with the titanium dioxide hydrosol to prepare the carbon material for sewage treatment; under the condition of low addition amount of the carbon material, good sewage treatment performance is realized for acidic sewage and alkaline sewage; after repeated regeneration and recycling, the sewage treatment performance can be kept well, the loss of active ingredients is less, the performance attenuation is reduced, and the long-term use performance is good; meanwhile, the possible pulverization problem in repeated regeneration and recycling of the carbon material can be effectively avoided.
(2) Through detection, the carbon material for sewage treatment is adopted to treat acidic wastewater, and COD is obtained after sewage treatment is carried out for 24 hours under visible light irradiation under the condition that the addition amount of the carbon material is 5% of the volume of the acidic wastewater cr The value of the chemical oxygen demand is reduced from 15600mg/L to 195-209mg/L, the concentration of ammonia nitrogen is reduced from 194mg/L to 2.2-2.6mg/L, the concentration of nickel ions is reduced from 8.3mg/L to 0.03-0.04mg/L, the concentration of zinc ions is reduced from 6.2mg/L to 0.01-0.02mg/L, and the concentration of copper ions is reduced from 5.5mg/L to 0.01-0.02mg/L; under the condition of low addition of carbon material, the COD of the acidic wastewater can be effectively reduced cr Value, and realizes effective adsorption on heavy metal and high COD cr The treatment effect of the acidic wastewater is good.
(3) Through detection, when the carbon material for sewage treatment is used for sewage treatment of alkaline wastewater, under the condition that the addition amount of the carbon material is 5% of the volume of the alkaline wastewater, after the sewage is treated for 10min, the content of methylene blue is reduced to 0.93-1.13mg/L from 49mg/L, and the removal rate of the methylene blue is 97.7-98.1%; under the condition of low addition of the carbon material, the organic pollutants in the alkaline wastewater can be effectively degraded, and the treatment effect on the alkaline organic wastewater is good.
(4) Through detection, the carbon material for sewage treatment is recycled for 8 times, and is used for treating acidic wastewater, namely COD cr The value is reduced from 15600mg/L to 241-260mg/L; the content of methylene blue is reduced from 49mg/L to 1.42-1.57mg/L, the removal rate of the methylene blue is 96.8-97.1%, and the carbon material has no pulverization problem; after repeated regeneration and reuse, the sewage treatment performance can be kept, the loss of active ingredients is less, the performance attenuation is reduced, and the long-term use performance is good.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of a carbon material for sewage treatment specifically comprises the following steps:
1. modification of carbon fibers
Adding polyacrylonitrile-based carbon fiber powder into a nitric acid solution with the volume 8 times that of the polyacrylonitrile-based carbon fiber powder, heating to 35 ℃ under the condition of stirring, carrying out heat preservation and reflux for 3 hours, filtering, and washing with sufficient deionized water until the solution is neutral; and (3) after heat preservation and drying at 110 ℃ for 6h, putting the mixture into 6 times of the volume of the first modified solution, heating to 40 ℃, performing ultrasonic dispersion for 1h, filtering out, washing for 2 times by using 8 times of volume of ethanol, washing to be neutral by using sufficient deionized water, and heat preservation and drying at 75 ℃ for 8h to obtain the modified carbon fiber.
Wherein, the mesh number of the polyacrylonitrile-based carbon fiber powder is 500 meshes.
The concentration of the nitric acid solution was 8wt%.
The first modified liquid is prepared by the following method, the silane coupling agent KH-570 is put into ethanol solution, after being mixed evenly, acetic acid is adopted to adjust the pH value to 4, and the first modified liquid is prepared.
In the first modified solution, the ratio of the silane coupling agent KH-570 to the ethanol solution in parts by weight is 5. The concentration of the ethanol solution was 90% (volume percent).
The ultrasonic power of ultrasonic dispersion is 800W, and the ultrasonic frequency is 30kHz.
2. Stock preparation
And (3) putting the modified carbon fiber into deionized water, and uniformly dispersing by ultrasonic to obtain a solution A. Wherein the weight ratio of the modified carbon fiber to the deionized water is 3.
And adding ferric chloride hexahydrate, sodium acetate trihydrate and cobalt acetate tetrahydrate into deionized water, and stirring until the ferric chloride hexahydrate, the sodium acetate trihydrate and the cobalt acetate tetrahydrate are completely dissolved to obtain a solution B. Wherein the weight ratio of ferric chloride hexahydrate, sodium acetate trihydrate, cobalt acetate tetrahydrate and deionized water is 1.3.
And adding the L-cysteine into deionized water, and stirring until the L-cysteine is completely dissolved to prepare a solution C. Wherein the weight ratio of the L-cysteine to the deionized water is 0.3.
And adding ascorbic acid into deionized water, and stirring until the ascorbic acid is completely dissolved to obtain solution D. Wherein the weight ratio of the ascorbic acid to the deionized water is 0.18.
3. Preparation of the first component
Adding the solution A into the solution B, uniformly mixing, stirring and dropwise adding the solution C at the dropwise adding rate of 3mL/min at the temperature of 20 ℃, and continuously stirring for 3 hours after the dropwise adding of the solution C is finished; then dripping the solution D at the dripping speed of 0.1mL/min, and after finishing dripping the solution D, carrying out ultrasonic dispersion for 20min; then transferring the mixture into a hydrothermal reaction kettle with a closed space, controlling the filling degree (the volume of liquid accounts for 60 percent of the total volume of the closed space in the hydrothermal reaction kettle), heating to 190 ℃, preserving heat, carrying out hydrothermal reaction for 8 hours, naturally cooling to normal temperature, filtering out solids, washing for 2 times by using ethanol with the volume being 8 times, washing for 2 times by using deionized water with the volume being 8 times, and then carrying out freeze drying to obtain the first component.
Wherein, the weight ratio of the solution A to the solution B to the solution C to the solution D is 1.
The ultrasonic power of ultrasonic dispersion is 600W, and the ultrasonic frequency is 35kHz.
4. Preparation of the second component
Putting zeolite powder and a second modification solution into a ball mill, controlling the ball-to-material ratio to be 5; and (3) placing the ball-milled material at 75 ℃ for heat preservation and drying to constant weight to obtain a second component.
Wherein the mesh number of the zeolite powder is 200 meshes.
The weight ratio of the zeolite powder to the second modification liquid is 1.2.
The second modified liquid is prepared by the following method that the silane coupling agent KH-550 and the silane coupling agent KH-570 are put into an ethanol solution and are mixed evenly to prepare the second modified liquid.
In the second modification liquid, the ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution in parts by weight is 4. The concentration of the ethanol solution was 85% (volume percent).
5. Shaping of
Uniformly mixing the first component, the second component and the titanium dioxide hydrosol, performing extrusion strip prefabrication and molding, placing in a nitrogen atmosphere environment, heating to 350 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain the carbon material for sewage treatment.
Wherein the ratio of the first component to the second component to the titanium dioxide hydrosol by weight parts is 70.
The titanium dioxide hydrosol is anatase type nano titanium dioxide hydrosol, the content of the titanium dioxide is 15wt%, and the particle size of the titanium dioxide is 10nm.
Example 2
A preparation method of a carbon material for sewage treatment specifically comprises the following steps:
1. modification of carbon fibers
Adding polyacrylonitrile-based carbon fiber powder into a nitric acid solution with the volume 9 times that of the polyacrylonitrile-based carbon fiber powder, heating to 40 ℃ under the condition of stirring, carrying out heat preservation and reflux for 4 hours, filtering, and washing with sufficient deionized water until the solution is neutral; and (3) after the heat preservation and drying at 120 ℃ for 7h, putting the mixture into the first modified liquid with the volume 7 times, heating to 45 ℃, carrying out ultrasonic dispersion for 1.5h, filtering, washing for 3 times by using ethanol with the volume 9 times, washing to be neutral by using sufficient deionized water, and carrying out heat preservation and drying at 80 ℃ for 9h to obtain the modified carbon fiber.
Wherein the mesh number of the polyacrylonitrile-based carbon fiber powder is 550 meshes.
The concentration of the nitric acid solution was 10wt%.
The first modified liquid is prepared by the following method, the silane coupling agent KH-570 is put into ethanol solution, after being mixed evenly, acetic acid is adopted to adjust the pH value to 4.5, and the first modified liquid is prepared.
In the first modified solution, the ratio of the silane coupling agent KH-570 to the ethanol solution in parts by weight is 7. The concentration of the ethanol solution was 92% (volume percent).
The ultrasonic power of the ultrasonic dispersion is 1100W, and the ultrasonic frequency is 32kHz.
2. Stock preparation
And (3) putting the modified carbon fiber into deionized water, and uniformly dispersing by ultrasonic to obtain a solution A. Wherein the weight ratio of the modified carbon fiber to the deionized water is 4.
And putting ferric chloride hexahydrate, sodium acetate trihydrate and cobalt acetate tetrahydrate into deionized water, and stirring until the ferric chloride, the sodium acetate trihydrate and the cobalt acetate tetrahydrate are completely dissolved to obtain solution B. Wherein the weight parts ratio of ferric chloride hexahydrate, sodium acetate trihydrate, cobalt acetate tetrahydrate and deionized water is (1.5).
And adding the L-cysteine into deionized water, and stirring until the L-cysteine is completely dissolved to prepare a solution C. Wherein the weight ratio of the L-cysteine to the deionized water is 0.32.
And adding ascorbic acid into deionized water, and stirring until the ascorbic acid is completely dissolved to obtain solution D. Wherein the weight ratio of the ascorbic acid to the deionized water is 0.19.
3. Preparation of the first component
Adding the solution A into the solution B, uniformly mixing, stirring at 25 ℃, dropwise adding the solution C at a dropwise adding rate of 4mL/min, and continuously stirring for 3.5h after dropwise adding of the solution C is finished; then dripping the solution D at the dripping speed of 0.15mL/min, and after finishing dripping the solution D, carrying out ultrasonic dispersion for 30min; then transferring the mixture into a hydrothermal reaction kettle with a closed space, controlling the filling degree (the volume of liquid accounts for 65 percent of the total volume of the closed space in the hydrothermal reaction kettle), heating to 195 ℃, preserving heat, carrying out hydrothermal reaction for 9 hours, naturally cooling to normal temperature, filtering out solids, washing for 3 times by using 9 times of ethanol, washing for 3 times by using 9 times of deionized water, and then freeze-drying to obtain the first component.
Wherein the ratio of the parts by weight of the solution A to the solution B to the solution C to the solution D is 1.
The ultrasonic power of the ultrasonic dispersion is 650W, and the ultrasonic frequency is 38kHz.
4. Preparation of the second component
Putting the zeolite powder and the second modification solution into a ball mill, controlling the ball-material ratio to be 6; and (3) placing the ball-milled material at 80 ℃, preserving heat and drying to constant weight to obtain a second component.
Wherein the mesh number of the zeolite powder is 250 meshes.
The weight part ratio of the zeolite powder to the second modification liquid is 1.
The second modified liquid is prepared by putting silane coupling agent KH-550 and silane coupling agent KH-570 into ethanol solution, and mixing to obtain the second modified liquid.
In the second modification liquid, the weight part ratio of a silane coupling agent KH-550 to a silane coupling agent KH-570 to an ethanol solution is 4.5. The concentration of the ethanol solution was 90% (volume percent).
5. Shaping of
Uniformly mixing the first component, the second component and the titanium dioxide hydrosol, granulating, performing, molding, placing in a nitrogen atmosphere environment, heating to 380 ℃ at a heating rate of 7 ℃/min, and preserving heat for 2.5 hours to obtain the carbon material for sewage treatment.
Wherein, the weight ratio of the first component to the second component to the titanium dioxide hydrosol is 72.
The titanium dioxide hydrosol is anatase type nano titanium dioxide hydrosol, the content of the titanium dioxide is 18wt%, and the particle size of the titanium dioxide is 15nm.
Example 3
A preparation method of a carbon material for sewage treatment specifically comprises the following steps:
1. modification of carbon fibers
Adding polyacrylonitrile-based carbon fiber powder into a nitric acid solution with the volume of 10 times, heating to 45 ℃ under the stirring condition, carrying out heat preservation and reflux for 5 hours, filtering, and washing with sufficient deionized water until the solution is neutral; and (3) after heat preservation and drying at 130 ℃ for 8h, putting the mixture into the first modified liquid with the volume of 8 times, heating to 50 ℃, performing ultrasonic dispersion for 2h, filtering out, washing for 3 times by using ethanol with the volume of 10 times, washing to be neutral by using sufficient deionized water, and heat preservation and drying at 85 ℃ for 10h to obtain the modified carbon fiber.
Wherein the mesh number of the polyacrylonitrile-based carbon fiber powder is 600 meshes.
The concentration of the nitric acid solution was 12wt%.
The first modified liquid is prepared by the following method that silane coupling agent KH-570 is put into ethanol solution, and after being mixed evenly, acetic acid is adopted to adjust the pH value to 5, thus preparing the first modified liquid.
In the first modified solution, the ratio of the silane coupling agent KH-570 to the ethanol solution in parts by weight is 8. The concentration of the ethanol solution was 95% (volume percent).
The ultrasonic power of ultrasonic dispersion is 1200W, and the ultrasonic frequency is 35kHz.
2. Stock preparation
And (3) putting the modified carbon fiber into deionized water, and uniformly dispersing by ultrasonic to prepare a solution A. Wherein the weight ratio of the modified carbon fiber to the deionized water is 5.
And adding ferric chloride hexahydrate, sodium acetate trihydrate and cobalt acetate tetrahydrate into deionized water, and stirring until the ferric chloride hexahydrate, the sodium acetate trihydrate and the cobalt acetate tetrahydrate are completely dissolved to obtain a solution B. Wherein the weight ratio of ferric chloride hexahydrate, sodium acetate trihydrate, cobalt acetate tetrahydrate and deionized water is 1.6.
And adding the L-cysteine into deionized water, and stirring until the L-cysteine is completely dissolved to prepare a solution C. Wherein the weight ratio of the L-cysteine to the deionized water is 0.35.
And adding ascorbic acid into deionized water, and stirring until the ascorbic acid is completely dissolved to obtain solution D. Wherein the weight ratio of the ascorbic acid to the deionized water is 0.2.
3. Preparation of the first component
Adding the solution A into the solution B, uniformly mixing, stirring and dropwise adding the solution C at the dropwise adding speed of 5mL/min at the temperature of 30 ℃, and continuously stirring for 4 hours after the dropwise adding of the solution C is finished; then dripping the solution D at the dripping speed of 0.2mL/min, and after finishing dripping the solution D, carrying out ultrasonic dispersion for 50min; then transferring the mixture into a hydrothermal reaction kettle with a closed space, controlling the filling degree (the volume of liquid accounts for 70 percent of the total volume of the closed space in the hydrothermal reaction kettle) to be 70 percent, heating to 200 ℃, carrying out thermal insulation for hydrothermal reaction for 10 hours, naturally cooling to normal temperature, filtering out solids, washing for 3 times by using 10 times of volume of ethanol, washing for 3 times by using 8-10 times of volume of deionized water, and then freeze-drying to obtain the first component.
Wherein, the weight ratio of the solution A to the solution B to the solution C to the solution D is 1.
The ultrasonic power of the ultrasonic dispersion is 700W, and the ultrasonic frequency is 40kHz.
4. Preparation of the second component
Putting zeolite powder and a second modification solution into a ball mill, controlling the ball-to-material ratio to be 7; and (3) placing the ball-milled material at 85 ℃, preserving heat and drying to constant weight to obtain a second component.
Wherein the mesh number of the zeolite powder is 300 meshes.
The weight ratio of the zeolite powder to the second modification liquid is 1.5.
The second modified liquid is prepared by putting silane coupling agent KH-550 and silane coupling agent KH-570 into ethanol solution, and mixing to obtain the second modified liquid.
In the second modification liquid, the weight part ratio of a silane coupling agent KH-550 to a silane coupling agent KH-570 to an ethanol solution is (5). The concentration of the ethanol solution was 95% (volume percent).
5. Shaping of
Uniformly mixing the first component, the second component and the titanium dioxide hydrosol, performing die pressing and prefabricating, placing in a nitrogen atmosphere environment, heating to 400 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 hours to obtain the carbon material for sewage treatment.
Wherein the ratio of the first component to the second component to the titanium dioxide hydrosol by weight part is 75.
The titanium dioxide hydrosol is anatase type nano titanium dioxide hydrosol, the content of the titanium dioxide is 20wt%, and the particle size of the titanium dioxide is 20nm.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference lies in that: 1) The carbon fiber modification step is omitted, and the unmodified polyacrylonitrile-based carbon fiber powder is directly used for the material preparation step; 2) In the step of preparing the raw materials, ferric chloride hexahydrate and sodium acetate trihydrate in the solution B are omitted.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference lies in that: 1) Material preparation steps are omitted; 2) The technical scheme for preparing the first component is modified in that ferric chloride hexahydrate and sodium acetate trihydrate are added into deionized water, stirring is carried out for 3.5 hours, modified carbon fibers are added, the mixture is uniformly dispersed and then transferred into a hydrothermal reaction kettle with a closed space, the filling degree is controlled to be 65%, the temperature is raised to 195 ℃, the temperature is kept for 9 hours, the mixture is naturally cooled to the normal temperature, solid matters are filtered out, the mixture is washed for 3 times by using 9 times of ethanol, washed for 3 times by using 9 times of deionized water, and then freeze drying is carried out to prepare the first component.
Wherein the weight ratio of ferric chloride hexahydrate, sodium acetate trihydrate, modified carbon fiber and deionized water is 3.
Test example 1
The carbon materials for wastewater treatment prepared in examples 1 to 3 and comparative examples 1 to 2 were examined for their performance in treating acidic wastewater. Specifically, sewage of certain industrial park of Shandong Shouguang is used as first test water, and the initial COD of the first test water cr The value is 15600mg/L, the ammonia nitrogen concentration is 194mg/L, the nickel ion concentration is 8.3mg/L, the zinc ion concentration is 6.2mg/L, the copper ion concentration is 5.5mg/L, and the pH value is 4.5.
The carbon material for wastewater treatment and the first test water of each example and comparative example were respectively charged into an industrial wastewater treatment apparatus, the amount of the carbon material added was controlled to be 5% by volume of the first test water, and COD in the wastewater was detected 24 hours after wastewater treatment under visible light irradiation cr Value and content of each heavy metal ion.
The specific results are as follows:
test example 2
The carbon materials for wastewater treatment obtained in examples 1 to 3 and comparative examples 1 to 2 were examined for their alkaline wastewater treatment performance. Specifically, sewage containing methylene blue dye is used as second test water, the content of methylene blue in the second test water is 49mg/L, and the pH value is 10.
The carbon material for wastewater treatment of each example and comparative example was mixed with the second test water at room temperature, and the amount of the carbon material added was controlled to be 5% by volume of the second test water, and then the NaClO solution was added to perform wastewater treatment at room temperature. After the sewage is treated for 10min, detecting the content of methylene blue in the second test water, and calculating the removal rate of the methylene blue.
Wherein the effective chlorine concentration in the NaClO solution is 10wt%; the amount of NaClO solution added per liter of second test water was 0.3mL.
The specific results are as follows:
test example 3
The carbon material after the completion of the sewage treatment in test example 1 and test example 2 was subjected to a regeneration treatment by an ethanol elution method and a high-temperature calcination method according to the prior art. The regenerated carbon material was recycled 7 times, and the regeneration treatment was performed after each sewage treatment test.
The carbon material which is recycled for 7 times is adopted to carry out sewage treatment on the first test water and the second test water, and the COD in the first test water after the sewage treatment is finished is detected cr A value; calculating the methylene blue removal rate according to the methylene blue content in the second test water; and observing whether the carbon material has pulverization.
The specific results are as follows:
it can be seen that in the embodiment of the invention, the polyacrylonitrile-based carbon fiber powder is modified, and the modified carbon fiber is used for preparing the first component; and a specific active ingredient combination and a preparation method are arranged in the first component; setting specific treatment on zeolite powder to prepare a second component; and the first component and the second component are matched with the titanium dioxide hydrosol to prepare the carbon material for sewage treatment; under the condition of low addition amount of the carbon material, good sewage treatment performance is realized for acidic sewage and alkaline sewage; after repeated regeneration and recycling, the sewage treatment performance can be kept well, the loss of active ingredients is less, the performance attenuation is reduced, and the long-term use performance is good; meanwhile, the possible pulverization problem in repeated regeneration and reutilization of the carbon material can be effectively avoided.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon material for sewage treatment is characterized by comprising the following steps: modifying carbon fibers, preparing materials, preparing a first component, preparing a second component and forming;
carrying out acid washing, water washing and drying on polyacrylonitrile-based carbon fiber powder, then putting the polyacrylonitrile-based carbon fiber powder into a first modification solution with the volume of 6-8 times, carrying out ultrasonic dispersion for 1-2h at the temperature of 40-50 ℃, and then carrying out alcohol washing, water washing and drying to obtain modified carbon fiber;
the first modified solution is prepared by the following method, adding a silane coupling agent KH-570 into an ethanol solution, uniformly mixing, and adjusting the pH value to 4-5;
preparing materials, namely putting the modified carbon fibers into deionized water, and uniformly dispersing to prepare a solution A;
putting ferric chloride hexahydrate, sodium acetate trihydrate and cobalt acetate tetrahydrate into deionized water, and completely dissolving to obtain solution B;
putting L-cysteine into deionized water, and completely dissolving to obtain solution C;
adding ascorbic acid into deionized water, and dissolving completely to obtain solution D;
the first component is prepared by adding the solution A into the solution B, uniformly mixing, stirring and dropwise adding the solution C at the temperature of 20-30 ℃, and continuously stirring for 3-4h after the dropwise adding of the solution C is finished; then dropwise adding the solution D, and after the dropwise adding of the solution D is finished, ultrasonically dispersing for 20-50min; then transferring the mixture into a closed space, controlling the filling degree to be 60-70%, heating to 190-200 ℃, preserving heat, carrying out hydrothermal reaction for 8-10h, naturally cooling to normal temperature, filtering out solids, washing for 2-3 times by using ethanol, washing for 2-3 times by using deionized water, and freeze-drying to obtain a first component;
the second component is prepared by ball-milling the zeolite powder and the second modification liquid and then drying;
the second modified solution is prepared by the following method, the silane coupling agent KH-550 and the silane coupling agent KH-570 are put into an ethanol solution and are uniformly mixed;
and (3) molding, namely uniformly mixing the first component, the second component and the titanium dioxide hydrosol, performing molding, placing in a nitrogen atmosphere environment, heating to 350-400 ℃, and preserving heat for 2-3 hours to obtain the carbon material for sewage treatment.
2. The method for preparing a carbon material for sewage treatment according to claim 1, wherein in the modification of the carbon fiber, the mesh number of polyacrylonitrile-based carbon fiber powder is 500-600 mesh;
the acid cleaning adopts nitric acid solution, and the concentration of the nitric acid solution is 8-12wt%;
the ultrasonic power of ultrasonic dispersion is 800-1200W, and the ultrasonic frequency is 30-35kHz.
3. The method for preparing a carbon material for wastewater treatment according to claim 1, wherein in the first modification solution, a ratio of a silane coupling agent KH-570 to an ethanol solution in parts by weight is 5-8; the concentration of the ethanol solution is 90-95%.
4. The preparation method of the carbon material for sewage treatment according to claim 1, wherein in the preparation material, the ratio of the modified carbon fiber in the solution A to the deionized water in parts by weight is 3-5;
the weight ratio of ferric chloride hexahydrate, sodium acetate trihydrate, cobalt acetate tetrahydrate and deionized water in the solution B is 1.3-1.6;
the weight part ratio of the L-cysteine to the deionized water in the solution C is 0.3-0.35;
the weight ratio of the ascorbic acid to the deionized water in the solution D is 0.18-0.2.
5. The method for preparing a carbon material for wastewater treatment according to claim 1, wherein in the preparing of the first component, a dropping rate of the solution C is 3 to 5mL/min; the dripping speed of the solution D is 0.1-0.2mL/min;
the ultrasonic power of ultrasonic dispersion is 600-700W, and the ultrasonic frequency is 35-40kHz.
6. The method for preparing a carbon material for wastewater treatment according to claim 1, wherein the ratio of parts by weight of the solution A, the solution B, the solution C and the solution D in the first component is 1.
7. The method for producing a carbon material for wastewater treatment according to claim 1, wherein in the second component, the zeolite powder has a mesh size of 200 to 300 mesh;
the weight ratio of the zeolite powder to the second modification liquid is 1.2-1.5.
8. The method for preparing the carbon material for wastewater treatment according to claim 1, wherein the second modification liquid comprises 4 to 5 parts by weight of a silane coupling agent KH-550, a silane coupling agent KH-570 and an ethanol solution; the concentration of the ethanol solution is 85-95%.
9. The method for producing a carbon material for wastewater treatment according to claim 1, wherein in the molding, the temperature rise rate is 5 to 10 ℃/min;
the first component, the second component and the titanium dioxide hydrosol have the weight part ratio of 70-75;
the titanium dioxide hydrosol is anatase type nano titanium dioxide hydrosol, the content of the titanium dioxide is 15-20wt%, and the particle size of the titanium dioxide is 10-20nm.
10. A carbon material for sewage treatment, characterized by being produced by the production method according to any one of claims 1 to 9.
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