CN111573901A - Method for treating fluorine-containing wastewater - Google Patents
Method for treating fluorine-containing wastewater Download PDFInfo
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Abstract
The invention discloses a method for treating fluorine-containing wastewater, which comprises the following steps: (1) adjusting the pH value of the fluorine-containing wastewater to 3-8, and adding a chemical defluorinating agent into the fluorine-containing wastewater for reaction; adding alkali to adjust the pH of the reaction solution to 6-9 after the reaction, adding polyacrylamide to perform a flocculation reaction, and performing solid-liquid separation to obtain a primary purified solution and primary filter residue; (2) and (3) dynamically adsorbing the primary purifying liquid by adopting modified strong-base anion resin, and deeply removing fluorine in the primary purifying liquid to obtain secondary purifying liquid. The method carries out advanced treatment on the fluorine in the wastewater by a chemical precipitation method and modified strong-base anion resin, and finally the fluorine content of the effluent is stably lower than 1 mg/L.
Description
Technical Field
The invention relates to a method for treating fluorine-containing wastewater, belonging to the technical field of wastewater treatment.
Background
Fluorine is one of the elements widely distributed in nature, and among all the elements, fluorine is ranked 13 in the earth's crust, and is mainly present as fluorite (CaF2), cryolite (Na3[ AlF6]), and fluorapatite (Ca10(PO4)6F 2). The fluorine has wide industrial application and can be used for synthesizing coolants such as Freon and the like; used for preparing fluorinating reagents (xenon difluoride and the like) and fluxing agents (cryolite and the like) in metal smelting, and the like; ClF3 and BrF3 can be used as oxidants of rocket fuels; used for preparing insecticide and fire-extinguishing agent, etc.
Trace fluorine is beneficial to preventing dental caries, and if the fluorine content in water is less than 0.5ppm, the incidence rate of dental caries can reach 70-90%. However, if the fluorine content in the drinking water exceeds 1ppm, the teeth are gradually stained and become brittle. When the fluorine content in the drinking water exceeds 4ppm, the human is susceptible to fluorosis, resulting in bone marrow malformation.
A large amount of fluorine-containing wastewater, waste residues and waste gases are discharged in the production process of a plurality of industries, and industrial wastewater containing fluoride is discharged in the processes of manufacturing fluorine-containing products, producing coke, producing electronic components, electroplating, producing glass and silicate, manufacturing steel and aluminum, processing metal, preserving wood, producing pesticides and fertilizers and the like. In the copper smelting industry alone, due to the exploitation of fluorine-containing ores in recent years, a large amount of industrial wastewater containing tens to hundreds of milligrams of fluorine is generated. Meanwhile, waste acid is generated in the copper smelting process, the acidity is high, pollution factors are many and are mixed, and the fluorine content is basically over 1 g/L.
Excessive fluorine not only causes serious harm to human body, but also causes toxic action to plants, and inhibits metabolism, photosynthesis, respiration and the like of the plants. More seriously, once fluorine enters the air, the fluorine is transferred along with the diffusion of gas and is mixed in rainwater or snow water to settle, so that the large-area pollution of the atmosphere, water and soil is caused, the buildings are damaged, and even the ozone layer is damaged. Therefore, the emission standards established by the nation for the waste gas of the fluorine-containing waste water are becoming stricter, which poses a great challenge to our control of fluorine pollution.
At present, a great deal of work has been carried out on the aspect of researching the treatment of the fluorine-containing wastewater at home and abroad, and CN 110078315A discloses a method for treating the fluorine-containing wastewater, which realizes the removal of fluorine ions in water by a chemical precipitation method, but the retention time is as long as 12h, and the removal effect is not described; CN 109250794 a discloses a fluorine-containing wastewater treatment system consisting of a dc power supply unit, a to-be-treated water pouring unit, a reaction unit, an anode unit, a cathode unit and a pH control unit. The system realizes waste utilization, takes the waste aluminum scraps as an anode unit, has good fluorine removal effect, but aims to generate cryolite instead of pure removal of fluorine in water, and the fluorine content in effluent cannot reach the emission standard; CN 104773877A discloses a method for treating fluorine-containing acidic wastewater, which comprises the steps of settling, filtering, adding calcium hydroxide and adjusting the pH value to 5-6, adding a mixture of the calcium hydroxide and polyaluminium chloride and adjusting the pH value to 7-8, and reducing the fluorine content of the filtered effluent to below 10 mg/L.
In recent years, the national requirements for environmental protection are more and more strict, the fluorine content in water is required to be determined by various emission standards, and the existing treatment processes are obviously difficult to meet the requirements, so that the development of an advanced treatment method with simple process and excellent effect is urgently needed.
Disclosure of Invention
In order to solve the problem that the prior art cannot deeply treat fluorine pollution, the invention aims to provide a method for treating fluorine-containing wastewater, which deeply treats fluorine in the wastewater through a chemical precipitation method and modified strong-base anion resin, and finally ensures that the fluorine content in the effluent is stably lower than 1 mg/L.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for treating fluorine-containing wastewater comprises the following steps:
(1) adjusting the pH value of the fluorine-containing wastewater to 3-8, and adding a chemical defluorinating agent into the fluorine-containing wastewater for reaction; adding alkali to adjust the pH of the reaction solution to 6-9 after the reaction, adding polyacrylamide to perform a flocculation reaction, and performing solid-liquid separation to obtain a primary purified solution and primary filter residue;
(2) and (3) dynamically adsorbing the primary purifying liquid by adopting modified strong-base anion resin, and deeply removing fluorine in the primary purifying liquid to obtain secondary purifying liquid.
Preferably, the fluorine-containing wastewater is generated in the copper smelting industry, wherein the concentration of fluorine ions is 1-60 mg/L.
Preferably, in the step (1), one or more of dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, dilute acetic acid, sodium carbonate, sodium hydroxide, calcium hydroxide, carbide slag and calcium oxide is used for adjusting the pH of the fluorine-containing wastewater.
Preferably, in the step (1), the chemical defluorination agent is one or more of polyaluminium chloride, aluminium sulfate, aluminium nitrate, lanthanum nitrate, cerium nitrate, lanthanum chloride, aluminium chloride, polyferric sulfate, ferric trichloride and ferric sulfate, and the mass ratio of the defluorination agent to fluorine in the fluorine-containing wastewater is 10-100: 1.
preferably, in the step (1), the alkali is one or more of sodium carbonate, sodium hydroxide, calcium hydroxide, carbide slag and calcium oxide.
Preferably, in the step (1), the polyacrylamide is a solution with a mass concentration of 1 to 2 per mill, and the adding amount is 1 to 5 mL/L.
Preferably, in the step (2), the specific modification process of the modified strongly basic anion resin is as follows: firstly, shaking and cleaning the strong-base anion resin with clear water for 20-30 min, and repeatedly cleaning for 2-3 times; then, oscillating and activating the strong-base anion resin for 1-2 hours by using an inorganic chemical agent, wherein the inorganic chemical agent is one or more of hydrochloric acid, sulfuric acid, calcium chloride, sodium hydroxide, sodium bicarbonate and sodium carbonate; and finally, modifying the strongly basic anion resin by using a modifying solution to obtain the modified strongly basic anion resin, wherein the modifying solution is one or more of aluminum sulfate, lanthanum nitrate, cerium nitrate, lanthanum chloride, lanthanum sulfate, aluminum chloride, polyaluminum chloride and cerium chloride. The strongly basic anionic resin of the present invention may be any conventional resin, such as D301, 201, etc., and the resin type is not particularly limited.
Preferably, in the step (2), the flow rate of the dynamic adsorption is 2-5 BV/h.
Preferably, in the step (2), after the modified strong-base anion resin is adsorbed and saturated, desorption is carried out by adopting a desorption solution, wherein the desorption solution is one or more of ammonia water, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydrosulfide and potassium hydroxide, the flow rate of the desorption solution is 1-5 BV/h, and the analysis time is 1-2 h.
Compared with the prior art, the invention has the following beneficial effects;
1. according to the invention, a one-stage chemical precipitation method is adopted to remove fluorine in the fluorine-containing wastewater to 5-10 mg/L, and then the primary purification liquid is subjected to deep defluorination by using modified strong-base anion resin, so that the fluorine in the fluorine-containing wastewater can be controlled to be below 1 mg/L.
2. The method has low requirement on the pH of the raw water of the fluorine-containing wastewater and wide application range.
3. The method has simple process flow, can be operated by slightly modifying the existing treatment facilities, and is suitable for industrial popularization.
Detailed Description
In order to better illustrate the present invention, the following will describe the method for treating fluorine-containing wastewater in detail with reference to the following examples. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
Taking fluorine-containing wastewater of a certain copper smelting plant, wherein the pH value of the fluorine-containing wastewater is 6.36, and the fluorine content is 21.68 mg/L.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing with clear water to neutrality, and modifying the strongly basic anion resin with a modifying solution to obtain the modified strongly basic anion resin for later use. The modified liquid is 10 wt% mixed solution compounded by 90% of aluminum sulfate and 10% of lanthanum nitrate.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.36mg/L by an ion selective electrode method;
(5) dynamically adsorbing the primary purifying liquid by using modified strong-base anion resin, wherein the flow rate of the primary purifying liquid is 2BV/h, taking the secondary purifying liquid after 30min, and measuring the residual fluorine content to be 0.46mg/L by using an ion chromatography;
(6) after the modified strong-base anion resin is adsorbed and saturated, 5 wt% of sodium hydroxide solution is adopted for desorption, the flow rate of the desorption solution is 1BV/h, and the desorption time is 2 h.
In order to verify the adsorption effect of the modified strong-base anion resin after the desorption on fluorine in the fluorine-containing wastewater, the modified strong-base anion resin was subjected to multiple adsorption saturation and desorption on the primary purified liquid in example 1, and the effect is shown in table 1.
TABLE 1 Desorption times and concentration of adsorbed effluent
From the results in table 1, it can be seen that: the adsorption effect of the modified strong-base anion resin on fluoride in the fluorine-containing wastewater after desorption is basically not different, and the resin can be repeatedly used.
Example 2
Taking fluorine-containing wastewater of a certain copper smelting plant, wherein the pH value of the fluorine-containing wastewater is 10.14, and the fluorine content is 13.8 mg/L.
Modification of the strongly basic anionic resin 201:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% sulfuric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium carbonate solution; rinsing with clear water to neutrality, and finally modifying the strongly basic anion resin by adopting 10 wt% of polyaluminium chloride solution to obtain the modified strongly basic anion resin for later use.
The specific treatment process comprises the following steps:
(1) because the pH value of raw water of the fluorine-containing wastewater is higher, firstly, 10 wt% of dilute sulfuric acid is adopted to adjust the pH value back to 6.5;
(2) adding 0.5g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 20 wt% solution prepared by combining 80% of polyaluminium chloride, 10% of polyferric sulfate and 10% of ferric trichloride;
(3) adding lime milk to adjust pH to 7.5, stirring and reacting for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1.5 per thousand, stirring for reaction for 2min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 3.14mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 4BV/h, the secondary purifying liquid is taken after 30min, and the residual fluorine content is measured by ion chromatography to be 0.29 mg/L.
Example 3
Taking fluorine-containing wastewater of a certain copper smelting plant, wherein the acidity is 0.1mol/L, and the fluorine content is 53.64 mg/L.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then carrying out shaking and activation on the strong-base anion resin for 1-2 h by using a 5 wt% sodium hydroxide solution; and finally, modifying the strongly basic anion resin by using a modifying solution to obtain the modified strongly basic anion resin for later use, wherein the modifying solution is a10 wt% solution prepared by compounding 70% of aluminum chloride and 30% of lanthanum chloride.
The specific treatment process comprises the following steps:
(1) adding sodium hydroxide to adjust the pH value to 5 because the acidity of the raw water of the fluorine-containing wastewater is higher;
(2) adding 2g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 20min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of aluminum nitrate and 20% of ferric trichloride;
(3) adding lime milk to adjust pH to 6.5, stirring and reacting for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 2 per thousand, stirring for reaction for 2min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 6.14mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 3BV/h, the secondary purifying liquid is taken after 30min, and the fluorine content is measured to be 0.67mg/L by ion chromatography.
Comparative example 1
The same procedure as in example 1 was repeated except that the fluorine-containing waste water was treated.
Unmodified strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing with clear water to neutrality for use.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.46mg/L by an ion selective electrode method;
(5) dynamically adsorbing the primary purifying liquid by unmodified strongly basic anion resin at a flow rate of 2BV/h, collecting the secondary purifying liquid after 30min, and measuring the residual fluorine content to be 4.01mg/L by ion chromatography.
Comparative example 2
The same procedure as in example 1 was repeated except that the fluorine-containing waste water was treated.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing with clear water to neutrality for later use, and finally modifying the strongly basic anion resin by adopting 10 wt% of phthalic anhydride to obtain the modified strongly basic anion resin for later use.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.54mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 2BV/h, the secondary purifying liquid is taken after 30min, and the residual fluorine content is measured by ion chromatography to be 2.96 mg/L.
Comparative example 3
The same procedure as in example 1 was repeated except that the fluorine-containing waste water was treated.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing with clear water to neutrality for later use, and finally modifying the strongly basic anion resin by adopting 10 wt% of dihydric alcohol to obtain the modified strongly basic anion resin for later use.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.41mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 2BV/h, the secondary purifying liquid is taken after 30min, and the residual fluorine content is measured by ion chromatography to be 2.48 mg/L.
Comparative example 4
The same procedure as in example 1 was repeated except that the fluorine-containing waste water was treated.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing with clear water to neutrality for later use, and finally modifying the strongly basic anion resin by adopting 10 wt% of mercaptoethanol to obtain the modified strongly basic anion resin for later use.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.73mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 2BV/h, the secondary purifying liquid is taken after 30min, and the residual fluorine content is 3.99mg/L by ion chromatography.
Comparative example 5
The same procedure as in example 1 was repeated except that the fluorine-containing waste water was treated.
Modification of the strongly basic anionic resin D301:
firstly, shaking and cleaning the strong-base anion resin for 20-30 min by using clean water, cleaning for 2-3 times, and then, carrying out shaking and activation on the strong-base anion resin for 1-2 h by using 5 wt% hydrochloric acid; then, oscillating and activating the strong-alkaline anion resin for 1-2 hours by adopting a 5 wt% sodium hydroxide solution; rinsing the resin with clear water to be neutral for later use, and finally modifying the strongly basic anion resin by adopting 10 wt% of triethylamine to obtain the modified strongly basic anion resin for later use.
The specific treatment process comprises the following steps:
(1) the pH value of the raw water of the fluorine-containing wastewater is within the range required by the invention, so that the adjustment back is not needed;
(2) adding 1g/L of chemical defluorinating agent into the fluorine-containing wastewater, and stirring for reacting for 15min, wherein the chemical defluorinating agent is a 30 wt% solution prepared by combining 80% of polyaluminium chloride and 20% of polyferric sulfate;
(3) adding liquid alkali to adjust the pH to 7.2, and stirring for reaction for 15 min;
(4) adding 1mL/L polyacrylamide with the mass concentration of 1 per thousand, stirring for reaction for 1min, performing solid-liquid separation, and measuring the residual fluorine content of the primary purified liquid to be 4.44mg/L by an ion selective electrode method;
(5) dynamic adsorption is carried out on the primary purifying liquid by adopting modified strong-base anion resin, the flow rate of the primary purifying liquid is 2BV/h, the secondary purifying liquid is taken after 30min, and the residual fluorine content is 3.69mg/L by ion chromatography.
Claims (9)
1. A method for treating fluorine-containing wastewater is characterized by comprising the following steps:
(1) adjusting the pH value of the fluorine-containing wastewater to 3-8, and adding a chemical defluorinating agent into the fluorine-containing wastewater for reaction; adding alkali to adjust the pH of the reaction solution to 6-9 after the reaction, adding polyacrylamide to perform a flocculation reaction, and performing solid-liquid separation to obtain a primary purified solution and primary filter residue;
(2) and (3) dynamically adsorbing the primary purifying liquid by adopting modified strong-base anion resin, and deeply removing fluorine in the primary purifying liquid to obtain secondary purifying liquid.
2. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: the fluorine-containing wastewater is generated in the copper smelting industry, wherein the concentration of fluorine ions is 1-60 mg/L.
3. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (1), one or more of dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, dilute acetic acid, sodium carbonate, sodium hydroxide, calcium hydroxide, carbide slag and calcium oxide are adopted to adjust the pH value of the fluorine-containing wastewater.
4. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (1), the chemical defluorination agent is one or more of polyaluminium chloride, aluminium sulfate, aluminium nitrate, lanthanum nitrate, cerous nitrate, lanthanum chloride, aluminium chloride, polyferric sulfate, ferric trichloride and ferric sulfate, and the mass ratio of the defluorination agent to fluorine in the fluorine-containing wastewater is 10-100: 1.
5. the method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (1), the alkali is one or more of sodium carbonate, sodium hydroxide, calcium hydroxide, carbide slag and calcium oxide.
6. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (1), the polyacrylamide is a solution with a mass concentration of 1-2 per mill, and the dosage is 1-5 mL/L.
7. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (2), the specific modification process of the modified strong-base anion resin is as follows: firstly, shaking and cleaning the strong-base anion resin with clear water for 20-30 min, and repeatedly cleaning for 2-3 times; then, oscillating and activating the strong-base anion resin for 1-2 hours by using an inorganic chemical agent, wherein the inorganic chemical agent is one or more of hydrochloric acid, sulfuric acid, calcium chloride, sodium hydroxide, sodium bicarbonate and sodium carbonate; and finally, modifying the strongly basic anion resin by using a modifying solution to obtain the modified strongly basic anion resin, wherein the modifying solution is one or more of aluminum sulfate, lanthanum nitrate, cerium nitrate, lanthanum chloride, lanthanum sulfate, aluminum chloride, polyaluminum chloride and cerium chloride.
8. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (2), the flow rate of the dynamic adsorption is 2-5 BV/h.
9. The method for treating fluorine-containing wastewater according to claim 1, characterized in that: in the step (2), desorbing by using a desorption solution after the modified strong-base anion resin is adsorbed and saturated, wherein the desorption solution is one or more of ammonia water, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydrosulfide and potassium hydroxide, the flow rate of the desorption solution is 1-5 BV/h, and the desorption time is 1-2 h.
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| CN115487785A (en) * | 2022-09-22 | 2022-12-20 | 浙江工业大学 | Resin-based lanthanum-cerium bimetallic nano-oxide composite material, preparation method thereof and application thereof in removing fluorinion in water |
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| CN113200624A (en) * | 2021-05-17 | 2021-08-03 | 紫金铜业有限公司 | Defluorination process for washing smelting flue gas wastewater |
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| CN115487785A (en) * | 2022-09-22 | 2022-12-20 | 浙江工业大学 | Resin-based lanthanum-cerium bimetallic nano-oxide composite material, preparation method thereof and application thereof in removing fluorinion in water |
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