CN114887588A - Method for preparing activated carbon loaded nano zero-valent iron material by using solid reducing agent - Google Patents
Method for preparing activated carbon loaded nano zero-valent iron material by using solid reducing agent Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the technical field of sewage treatment and environmental remediation, and particularly relates to a method for preparing an active carbon-loaded nano zero-valent iron material by using a solid reducing agent. The method comprises the following steps: cleaning and drying activated carbon, adding ferrous sulfate heptahydrate into deoxygenated ultrapure water, adding activated carbon, oscillating, ultrasonically treating and standing, adding sodium borohydride solid in batches while stirring and introducing nitrogen, continuously stirring and filtering, cleaning a filtering product by using deoxygenated ultrapure water and absolute ethyl alcohol, and then drying in vacuum to obtain the activated carbon loaded nano zero-valent iron material. The invention adopts a mode of adding the solid reducing agent, so that the nano zero-valent iron particles are smaller, the loading capacity is larger, and the adsorption capacity to cadmium is greatly improved.
Description
Technical Field
The invention belongs to the technical field of material preparation and water treatment, and particularly relates to a preparation method of an activated carbon loaded nano zero-valent iron material.
Background
With the development of socioeconomic, environmental pollution is increasingly serious. Cadmium is a common heavy metal in water and has high toxicity and carcinogenicity. Cadmium is a non-essential element for human bodies, and is mainly derived from the discharge of industrial wastewater such as mining, electroplating, batteries, smelting, dyes and the like. Compared with other heavy metals, the cadmium ions have high fluidity, are easy to be absorbed by plants, and can be enriched in human bodies through food chains, and even the low-concentration cadmium in natural water bodies can cause great harm to the health and the ecological environment of the human bodies, so the cadmium-containing wastewater needs to be effectively treated before being discharged.
As a green and economic environment restoration technology, the nano zero-valent iron has larger specific surface area and higher reduction activity than common zero-valent iron and is a hotspot in the current environment restoration field. However, the preparation process of the nano zero-valent iron is complex, and the powdery nano zero-valent iron is easy to agglomerate when being used alone, so that the application of the nano zero-valent iron in environmental remediation is limited. The preparation method of dispersing the nano zero-valent iron in the activated carbon overcomes the defects that the nano zero-valent iron is easy to agglomerate and is difficult to separate when the nano zero-valent iron is simply used in the prior art.
At present, methods for loading zero-valent iron to activated carbon mainly include liquid-phase reduction methods, carbothermic methods, pyrolysis methods, ball milling methods, and the like. Among them, the liquid phase reduction method is the most commonly used method. CN103721715B discloses a method for preparing a loaded activated carbon nano zero-valent iron material by a liquid phase reduction method, in which a reducing agent sodium borohydride solution is mainly added to a ferrous sulfate solution of activated carbon, but the adsorption amount of nano zero-valent iron is not measured. CN112808232B discloses a preparation method and application of an activated carbon loaded nano zero-valent iron material, which mainly comprises the steps of dissolving and drying the impregnated activated carbon by ferrous sulfate, and then adding the activated carbon into an absolute ethyl alcohol solution of sodium borohydride in batches.
The liquid phase reduction method comprises the steps of loading an iron compound on a porous carbon material carrier in a mode of adsorption or deposition and the like, and reducing iron ions into zero-valent iron by using a strong reducing agent sodium borohydride solution. However, the price of the reducing agent is relatively high, sodium borohydride can react with water, and the solution needs to be prepared for use at present, so that the application of a liquid phase reduction method in the active carbon loaded nano zero-valent iron is limited to a certain extent.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems of loss of reducing agent sodium borohydride in the most widely used liquid phase reduction method and iron ion adsorption caused by adding of sodium borohydride solution in the prior art, the invention provides a method for preparing an active carbon-supported nano zero-valent iron material by using a solid reducing agent, and the method can simply and effectively load nano zero-valent iron on active carbon.
The technical scheme is as follows: a method for preparing an activated carbon-loaded nano zero-valent iron material by using a solid reducing agent comprises the following steps:
preparing activated carbon: washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven;
preparing a reaction solution: adding ferrous sulfate heptahydrate into deoxygenated ultrapure water, stirring until the ferrous sulfate heptahydrate is completely dissolved, adding granular activated carbon, oscillating, ultrasonically treating, and standing;
adding a reducing agent: placing the reaction solution on a magnetic stirrer, stirring, continuously introducing nitrogen, adding a solid reducing agent after the reaction solution is stabilized, and continuously stirring for 20-80min to obtain an activated carbon loaded nano zero-valent iron material mixed solution;
separating the activated carbon loaded nano zero-valent iron material: filtering the mixed liquid of the activated carbon loaded nano zero-valent iron material, respectively cleaning the filtered product with deoxygenated ultrapure water and absolute ethyl alcohol for three times, and then carrying out vacuum freeze drying for 18-24h to obtain the activated carbon loaded nano zero-valent iron material.
As a further technical scheme, the granular activated carbon in the step of preparing the activated carbon is 16-32 meshes, and the addition amount of the granular activated carbon is 100 g/L.
As a further technical scheme, the addition amount of the ferrous sulfate heptahydrate in the prepared reaction liquid is 4-33.3 g/L.
As a further technical scheme, in the preparation of reaction liquid, ferrous sulfate heptahydrate is added into a mixed solution of deoxidized ultrapure water and ethanol, polyethylene glycol 4000 is added after stirring till complete dissolution, stirring is continued till complete dissolution, granular activated carbon is added, and then oscillation, ultrasonic treatment and standing are carried out;
as a further technical scheme, in the preparation reaction solution, the addition amount of polyethylene glycol 4000 is 0-20g/L, and the deoxygenated ultrapure water: ethanol-10: 0-5: 5.
As a further technical scheme, in the preparation of the reaction solution, the ultrasonic time is 2-6h, and the standing time is 5-6 h.
As a further technical scheme, in the reducing agent, the solid reducing agent is sodium borohydride or potassium borohydride.
As a further technical scheme, in the reducing agent adding process, the solid reducing agent is added in 3-5 times, and the interval of each time is 8-10 s.
As a further technical scheme, the solid reducing agent is added into the reducing agent, and the adding amount of the solid reducing agent is 20-80 g/L.
As a further technical scheme, in the separation of the activated carbon loaded nano zero-valent iron material, nitrogen is introduced into the deoxidized ultrapure water for 30min before use.
The application of the activated carbon loaded nano zero-valent iron material in removing cadmium ions in sewage.
Compared with the prior art, the invention has the beneficial effects and advantages that:
1. according to the method, the reducing agent is directly added into the reaction system to prepare the activated carbon loaded nano zero-valent iron material, and the concentration of the reducing agent in the reaction system is increased under the condition of unchanged adding amount by directly adding the solid reducing agent into the reaction system, so that the reaction efficiency is higher, and the reaction aging time is shorter.
2. The active carbon-loaded nano zero-valent iron material prepared by adding the reducing agent into the solid has a simpler preparation process, is more beneficial to industrial production, and avoids the reaction of the reducing agent and water to a certain extent.
3. The active carbon loaded nano zero-valent iron material prepared by adding the reducing agent into the solid has smaller nano zero-valent iron particles loaded on the active carbon and larger load capacity, thereby greatly improving the adsorption capacity of the active carbon to cadmium.
4. The traditional liquid phase reduction method for preparing the nano zero-valent iron material usually needs to add a dispersing agent and ethanol to improve the dispersion degree of the zero-valent iron in a carrier, and the active carbon-loaded nano zero-valent iron material prepared by adding the reducing agent into the solid can obtain better adsorption effect even if the dispersing agent and the ethanol are not added.
Drawings
Fig. 1 shows the adsorption capacity and removal rate of the active carbon loaded nano zero-valent iron material with 8 different carbon-iron ratios, which is prepared and obtained in example 1 of the present invention, on cadmium ions with the same concentration.
Fig. 2 shows the adsorption amount and removal rate of the 7 kinds of activated carbon-loaded nanoscale zero-valent iron materials with different ultrasonic times, which are prepared and obtained in example 2 of the present invention, on cadmium ions with the same concentration.
FIG. 3 shows the adsorption capacity and removal rate of the 7 active carbon-loaded nanoscale zero-valent iron materials with different reducing agent addition amounts, which are obtained by the preparation of embodiment 3 of the present invention, to cadmium ions with the same concentration.
Fig. 4 shows the adsorption amount and removal rate of the 7 kinds of activated carbon-loaded nanoscale zero-valent iron materials with different stirring times on cadmium ions with the same concentration, which are prepared and obtained in example 4 of the present invention.
FIG. 5 shows the adsorption capacity and removal rate of the activated carbon-loaded nanoscale zero-valent iron material with 10 different dispersant addition amounts, which is obtained by the preparation of example 5 of the present invention, to cadmium ions with the same concentration.
Fig. 6 shows the adsorption amount and removal rate of cadmium ions with the same concentration by 6 different hydroalcoholic specific active carbon-loaded nano zero-valent iron materials prepared in example 6 of the present invention.
FIG. 7 is a graph showing the adsorption effect of example 7, comparative example 1, comparative example 2, comparative example 3, and comparative example 4 on cadmium ions of the same concentration.
FIG. 8 is an SEM image of activated carbon (5000X activated carbon on the left 1; 30000X activated carbon on the left 2).
FIG. 9 is an SEM image of an activated carbon-supported nano zero-valent iron material prepared using a liquid phase method (5000 times the left 1 for nano zero-valent iron/activated carbon prepared in comparative example 4 and 30000 times the left 2 for nano zero-valent iron/activated carbon prepared in comparative example 4).
FIG. 10 is an SEM image of a solid reducing agent prepared activated carbon supported nano zero-valent iron material (5000 times for the left 1 and example 7 for the left 2; 30000 times for the left 2).
Detailed Description
Example 1:
1. preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 3.33g, 2.00g, 1.43g, 1.11g, 0.91g, 0.77g, 0.67g and 0.40g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate was 3: 1, 5:1, 7: 1, 9: 1, 11: 1, 13: 1, 15:1 and 25: 1), respectively, were charged into the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol 4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 3 hours, standing for 6 hours after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding 5g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished to fully react. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. Measuring the adsorption capacity and removal rate of the activated carbon loaded nano zero-valent iron material to cadmium ions with the same concentration
0.1g of the 8 kinds of activated carbon-loaded nano zero-valent iron materials with different carbon-iron ratios prepared in example 1 are respectively weighed into a series of 150ml conical flasks, and the conical flasks are filled with cadmium ion solutions with the volume of 50ml, the pH value of 5 and the concentration of 100 mg/L. Oscillating and adsorbing for 24h under the conditions that the temperature is 30 ℃ and the oscillating rotation speed is 200 r/min. Then, the supernatant was filtered with a syringe filter (0.22 μm filter), the concentration of cadmium remaining in the filtrate was measured with an inductively coupled plasma emission spectrometer (ICP-OES) and the removal rate and the amount of adsorption were calculated, and the experiment was repeated three times to take an average value.
The adsorption capacity and removal rate of the activated carbon loaded nano zero-valent iron material with different carbon-iron ratios to cadmium ions with the same concentration are shown in figure 1.
The result of figure 1 shows that the removal rate of cadmium ions in the water body is the highest when the mass ratio of the activated carbon to the ferrous sulfate heptahydrate is 15: 1.
Example 2:
1. preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 1.11g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate is 9: 1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, performing ultrasonic treatment for 0h, 1h, 2h, 3h, 4h, 5h and 6h respectively, and standing for 6h after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding 5g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished to fully react. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. Adsorption capacity and removal rate of active carbon loaded nano zero-valent iron material on cadmium ions with same concentration in different ultrasonic time
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 2.
The result of fig. 2 shows that the state of the highest cadmium ion removal rate can be achieved when the ultrasonic time is 1h, and the cadmium ion removal rate cannot be remarkably improved by continuously lengthening the ultrasonic time.
Example 3:
1. preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 1.11g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate is 9: 1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 3 hours, standing for 6 hours after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding sodium borohydride solids with the total amount of 2g, 3g, 4g, 5g, 6g, 7g and 8g into the conical flask at intervals of 10s for three times respectively under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished to fully react. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. Adsorption capacity and removal rate of active carbon loaded nano zero-valent iron material with different reducing agent addition amounts on cadmium ions with same concentration
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 3.
The results in FIG. 3 show that the removal rate of cadmium ions is gradually increased with the addition of the solid reducing agent.
Example 4:
1. preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 1.11g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate is 9: 1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 3 hours, standing for 6 hours after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding 5g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and stirring for 20min, 30min, 40min, 50min, 60min, 70min and 80min respectively after the addition is finished to fully react. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. Adsorption capacity and removal rate of active carbon loaded nano zero-valent iron material on cadmium ions with same concentration in different stirring time
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 4.
The results of fig. 4 show that the stirring time after adding the solid reducing agent has no significant influence on the removal rate of cadmium ions.
Example 5:
1. preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 0.67g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate was 15:1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0g, 0.02g, 0.06g, 0.1g, 0.3g, 0.5g, 0.7g, 1g, 1.5g, 2.0g of polyethylene glycol-4000 was added to the flask, and stirred to dissolve completely. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 1h, standing for 6h after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
And (2) placing the conical flask on a magnetic stirrer for rapid stirring, continuously introducing nitrogen, adding 8g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished so as to enable the reaction to be full. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. The adsorption capacity and removal rate of the activated carbon loaded nano zero-valent iron material to cadmium ions with the same concentration are different in the adding amount of the dispersing agent
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 5.
The results in fig. 5 show that the material prepared without the addition of the dispersant polyethylene glycol 4000 still has a good effect of removing contaminants when a solid reducing agent is used.
Example 6
1. Preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of each solution (ultrapure water: absolute ethyl alcohol: 10:0, 9: 1, 8: 2, 7: 3, 6: 4, 5: 5) was taken and added to a 250ml wide-mouth flask, and the solution was added to the flask0.67g of ferrous sulfate heptahydrate (the mass ratio of the activated carbon to the ferrous sulfate heptahydrate is 15:1 respectively) is added, and the mixture is stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated active carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 1h, and standing for 6h after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
And (2) placing the conical flask on a magnetic stirrer for rapid stirring, continuously introducing nitrogen, adding 8g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished so as to enable the reaction to be full. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. The adsorption capacity and removal rate of the activated carbon loaded nano zero-valent iron material to cadmium ions with the same concentration are different in the adding amount of the dispersing agent
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 6.
The results in fig. 5 show that the material prepared without the addition of ethanol still has a good removal effect on contaminants when using a solid reducing agent.
Example 7
1. Preparation of active carbon loaded nano zero-valent iron material
Washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 0.67g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate was 15:1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 1h, standing for 6h after ultrasonic treatment to enable Fe 2+ Fully absorbed in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding 8g of sodium borohydride solid into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished to ensure that the reaction is full. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product for three times by using deoxygenated ultrapure water and absolute ethyl alcohol, and finally, carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
2. The adsorption amount and removal rate of the activated carbon-supported nano zero-valent iron material prepared in example 7 on cadmium ions were measured
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 7.
Comparative example 1:
washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven at 105 ℃ for 24h to constant weight. 100ml of ultrapure water was taken and charged into a 250ml wide-mouth flask, and 0.67g of ferrous sulfate heptahydrate (the mass ratio of activated carbon to ferrous sulfate heptahydrate was 15:1, respectively) was added to the flask, and stirred to completely dissolve the ferrous sulfate heptahydrate. 0.1g of polyethylene glycol-4000 was added to the flask and stirred to completely dissolve it. Adding 10g of treated activated carbon into a conical flask, shaking to uniformly disperse the biochar, then carrying out ultrasonic treatment for 1h, standing for 6h after ultrasonic treatment to enable Fe 2+ Fully adsorb in the activated carbon.
Placing the conical flask on a magnetic stirrer, quickly stirring, continuously introducing nitrogen, adding 21.2ml of 10mol/L sodium borohydride liquid (the amount of sodium borohydride substances in the reaction system is the same as that in example 7) into the conical flask at intervals of 10s for three times under the nitrogen atmosphere and magnetic stirring, and continuously stirring for 50min after the addition is finished to ensure that the reaction is full. And after the reaction is finished, filtering the obtained mixed solution, respectively cleaning the filtered product with deoxygenated ultrapure water and absolute ethyl alcohol for three times, and finally carrying out vacuum freeze drying on the obtained solid for 18 hours to obtain the activated carbon loaded nano zero-valent iron material.
The experimental procedure was as in example 1.
The results of the experiment are shown in FIG. 7.
Comparative example 2:
the procedure and procedure were the same as in comparative example 1, except that a total of 52.9ml of 4mol/L sodium borohydride liquid was added to the flask.
The results of the experiment are shown in FIG. 7.
Comparative example 3:
the procedure and procedure were the same as in comparative example 1, except that 70.5ml of a total amount of 3mol/L sodium borohydride liquid was added to the flask.
The results of the experiment are shown in FIG. 7.
Comparative example 4:
the procedure and procedure were the same as in comparative example 1, except that a total of 105.8ml of 2mol/L sodium borohydride liquid was added to the flask.
The results of the experiment are shown in FIG. 7.
The amounts of sodium borohydride material charged in example 7 above and comparative examples 1, 2, 3 and 4 were all equal.
The result of fig. 7 shows that the removal rate of cadmium ions can be significantly improved by adopting the adding manner of the solid reducing agent, and under the condition of a certain amount of sodium borohydride, the higher the concentration of sodium borohydride is, the higher the removal rate of cadmium ions is, and the removal rate of 8g of solid sodium borohydride to cadmium ions is increased by 10% compared with the highest concentration (10 mol/L).
Further, the SEM structure diagrams of fig. 8, 9, and 10 show that the density of the nano zero-valent iron material on the activated carbon-supported nano zero-valent iron material prepared by using the solid reducing agent is large, the distribution is uniform, and the particle size of the solid addition is smaller than that of the liquid addition particle nano zero-valent iron material, indicating that the material prepared by the method has a strong adsorption effect on the pollutants.
It should be noted that the above-mentioned embodiments are only illustrative embodiments of the present invention, and are not intended to limit the scope of the present invention. Any equivalent changes and modifications of the invention without departing from the spirit and principles of the invention should be considered within the scope of the invention.
Claims (10)
1. A method for preparing an activated carbon-loaded nano zero-valent iron material by using a solid reducing agent is characterized by comprising the following steps of:
preparing activated carbon: washing the granular activated carbon with deionized water to remove impurities, and drying in an electrothermal blowing drying oven;
preparing a reaction solution: adding ferrous sulfate heptahydrate into deoxygenated ultrapure water, stirring until the ferrous sulfate heptahydrate is completely dissolved, adding granular activated carbon, oscillating, ultrasonically treating, and standing;
adding a reducing agent: placing the reaction liquid on a magnetic stirrer, stirring, continuously introducing nitrogen, adding a solid reducing agent after the reaction liquid is stabilized, and continuously stirring for 20-80min to obtain an activated carbon loaded nano zero-valent iron material mixed liquid;
separating the activated carbon loaded nano zero-valent iron material: filtering the mixed solution of the activated carbon loaded nano zero-valent iron material, respectively cleaning the filtered product with deoxygenated ultrapure water and absolute ethyl alcohol for three times, and then carrying out vacuum freeze drying for 18-24h to obtain the activated carbon loaded nano zero-valent iron material.
2. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein the granular activated carbon is 16-32 meshes, and the addition amount of the granular activated carbon is 100 g/L.
3. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein the addition amount of ferrous sulfate heptahydrate in the reaction solution is 4-33.3 g/L.
4. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein ethanol and polyethylene glycol 4000 are added into the reaction solution.
5. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 4, wherein the addition amount of the polyethylene glycol 4000 is 0-20g/L, and the deoxidized ultrapure water: ethanol-10: 0-5: 5.
6. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein in the preparation of the reaction solution, the ultrasonic time is 2-6 hours, and the standing time is 5-6 hours.
7. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein in the step of adding the reducing agent, the solid reducing agent is sodium borohydride or potassium borohydride.
8. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein the solid reducing agent is added in 3-5 times at an interval of 8-10 s.
9. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to claim 1, wherein the solid reducing agent is added in an amount of 20-80 g/L.
10. The method for preparing the activated carbon-supported nano zero-valent iron material by using the solid reducing agent according to any one of claims 1 to 9, wherein the method is used for removing cadmium ions in a water body.
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