CN115010234B - Method for removing fluorine from solution by utilizing gaseous fluorine removing agent and gaseous fluorine removing agent - Google Patents
Method for removing fluorine from solution by utilizing gaseous fluorine removing agent and gaseous fluorine removing agent Download PDFInfo
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- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2101/00—Nature of the contaminant
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for removing fluorine from a solution by using a gaseous fluorine removing agent, which comprises the following steps: adjusting the pH value of the solution to be defluorinated to be more than 2; diluting and fully mixing the gaseous defluorinating agent by using inert gas, and introducing the diluted gaseous defluorinating agent into a solution to be defluorinated for defluorination reaction; and after the defluorination reaction is finished, adding a flocculating agent for precipitation, and filtering the solution to obtain defluorination residues and a defluorination solution. The defluorination process is simple to operate, easy to control, low in cost and easy to operate; taking the fluorine-containing solution generated in the waste battery recovery process as an example, after the fluorine-removing reagent is used for treatment, the removal rate of fluorine in the solution reaches more than 90 percent. The gaseous defluorinating agent is also disclosed, and is a combination of any two or more of gaseous titanium tetrachloride, silicon tetrachloride, cesium chloride, tin tetrachloride, aluminum chloride, bismuth chloride and ferric chloride. The gaseous defluorinating agent has the advantages of simple component composition, low cost and environmental protection.
Description
Technical Field
The invention belongs to the field of development of a defluorination reagent and defluorination of solution, and particularly relates to removal of fluorine in a fluorine-containing solution generated in a wet recovery process of waste power batteries and research and development of the defluorination reagent.
Background
The fluorine-containing wastewater is used as common industrial wastewater, and relates to the fields of metal smelting, cement, aluminum electrolysis, ceramics, semiconductors and the like, and the rapid development of the industry causes the fluorine-containing wastewater to cause increasingly serious damage to the environment. In addition, in the metallurgical process, the solution contains fluorine, so that the performance of a subsequent smelting process and a product can be seriously influenced. Precipitation was the earliest method of solution defluorination used, but Ca 2- And F - Formation of CaF 2 The reaction time is longer, and even the generation of precipitate is inhibited by certain anions sometimes, so that the fluorine concentration of the treated effluent is higher, generally between 20 and 50 mg/L.
Patent document CN201611136085.1 discloses a method for removing fluorine and silicon ions from nickel, cobalt and manganese sulfate solution, which mainly adopts organic extraction method to purify fluorine-containing nickel, cobalt and manganese sulfate solution. Patent document CN201910151667.4 discloses a process for removing fluorine from fluorine-containing zinc sulfate solution, which comprises dissolving fluorine-containing zinc sulfateAfter the solution is preheated, sulfuric acid and calcium carbonate are sequentially added to carry out defluorination on the solution; the precipitation method used was the earliest method of solution defluorination used, but Ca 2- And F - Formation of CaF 2 The reaction time is longer, and even the generation of precipitate is inhibited by certain anions sometimes, so that the fluorine concentration of the treated effluent is higher, generally between 20 and 50 mg/L. Patent document CN202010466004.4 discloses a method for removing fluorine from a mixed rare earth chloride solution by acid-base combination treatment, which is to add soluble carbonate in the process of removing fluorine to accurately control the pH value of the solution system by stages so as to further remove fluorine from the solution. Patent document CN201910667532.3 discloses a fluorine ion solution fluorine removal method, which mainly comprises adding high-silicon zinc oxide ore to react with the solution and then removing fluorine. Patent document CN201510187634.7 discloses a method for removing fluorine from sodium tungstate solution, which mainly comprises adding excessive calcium carbonate into sodium tungstate solution to react with fluorine, and adding excessive ferrous sulfate and ferrous hydroxide after the reaction is completed to promote flocculation of precipitate. Patent document CN201911399832.4 discloses a method for deeply removing fluorine from LiCl solution recovered from waste batteries, which mainly removes fluorine from the solution by adding a composite material prepared from alumina, porous carbon and a small amount of rare earth elements as a remover. The patent document with the patent application number of CN202011636165.X discloses a method for recovering LiHCO from waste lithium ion batteries 3 Method for deeply removing fluorine from solution by adding LiHCO 3 Adding defluorinating agent (acid activated composite material prepared from aluminum oxide, butyl titanate, zirconium sulfate and nitrogen-containing compound) into the solution, and mixing with CO 2 And regulating the reaction pH value by using gas to remove fluorine. Patent application No. CN201910998250.1 proposes a method for removing fluorine in a nickel-cobalt-manganese solution, which is to remove fluorine in the nickel-cobalt-manganese solution by using an aluminum-containing solution obtained by dissolving a current collector.
In general, for the removal of fluorine in a solution, the prior art has the disadvantages of complex fluorine removal process, long flow, complex composition of a fluorine removal agent, high requirement on pH control of the solution in the fluorine removal process, difficulty in realizing accurate control of the process by adopting various solid or liquid fluorine removal agents or pH regulators, and serious influence on the fluorine removal effect of the fluorine removal agent along with the progress of fluorine removal reaction in the fluorine removal process. Therefore, the fluorine removal agent with simple composition is provided, and a method with simple fluorine removal process, short flow, easy control and good fluorine removal effect is developed, which has very important significance in the field.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background art, and provide a method which has simple fluorine removal process, short flow, easy control and good fluorine removal effect, and a fluorine removal agent with simple composition.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for removing fluorine from a solution using a gaseous fluorine removal agent, comprising the steps of:
(1) Adjusting the pH value of the solution to be defluorinated to be more than 2;
(2) Diluting and fully mixing the gaseous defluorinating agent by using inert gas, and introducing the diluted gaseous defluorinating agent into a solution to be defluorinated for defluorination; the gaseous defluorinating agent is gaseous chloride, and the gaseous chloride is the combination of any two or more of titanium tetrachloride, silicon tetrachloride, cesium chloride, tin tetrachloride, aluminum chloride, bismuth chloride and ferric chloride;
(3) And after the defluorination reaction is finished, adding a flocculating agent for precipitation, and filtering the solution to obtain defluorination residues and a defluorination solution.
In the method for removing fluorine from the solution by using the gaseous fluorine removal agent, in the step (1), the solution to be subjected to fluorine removal is preferably a fluorine-containing solution generated in the wet recovery process of the waste power battery, wherein the fluorine-containing solution contains 1 to 5g/L of Li and 0.2 to 0.8g/L of F.
Preferably, in the step (1), the pH value of the solution to be subjected to defluorination is adjusted to 7 to 8.
Preferably, in the step (2), when the gaseous fluorine removing agent is diluted by using an inert gas, the mass of the gaseous fluorine removing agent is controlled to be more than 20% of the total mass of the gas, and the inert gas is any one or combination of more of argon and nitrogen.
Preferably, in the step (2), when the diluted gaseous fluorine removal agent is introduced into the solution to be subjected to fluorine removal, the introduction amount of the diluted gaseous fluorine removal agent is controlled according to 2 to 80mL/min of the diluted gaseous fluorine removal agent introduced into each liter of the solution, the temperature of the fluorine removal reaction is controlled to be 60 to 95 ℃, and the time of the fluorine removal reaction is 30 to 240min.
More preferably, in step (2), sodium hydroxide or sulfuric acid is used to adjust the pH of the solution during the defluorination reaction and maintain the pH of the solution at a value greater than 2.5.
Preferably, in the step (3), the flocculating agent comprises any one or more of polyacrylamide, polyacrylic acid, sodium polyacrylate and calcium polyacrylate, and the addition amount of the flocculating agent is 5 mg/L-25 mg/L.
Based on a general inventive concept, the invention also provides a gaseous defluorinating agent, wherein the gaseous defluorinating agent is gaseous chloride, and the gaseous chloride is a combination of any two or more of titanium tetrachloride, silicon tetrachloride, cesium chloride, tin tetrachloride, aluminum chloride, bismuth chloride and ferric chloride.
Preferably, the gaseous chloride is a combination of any two or more of titanium tetrachloride, silicon tetrachloride, tin tetrachloride and aluminum chloride.
More preferably, the gaseous defluorinating agent consists of gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous tin tetrachloride and gaseous aluminum chloride according to the mass ratio of 10-80: 5-90: 0-25: 0-40.
The method adopts gaseous chloride as a gaseous fluorine removal agent, and when the gaseous chloride is introduced into a solution to be subjected to fluorine removal, the gaseous chloride directly reacts with fluorine in the solution; on the other hand, the gaseous chloride can undergo hydrolysis reaction, and due to the adoption of the gaseous chloride, the adsorbent generated by hydrolysis can immediately adsorb fluorine in the solution, and the adsorbent capable of adsorbing fluorine can be used as a crystal nucleus for chloride hydrolysis to generate a fresh adsorbent to continuously adsorb fluorine, and the steps are repeated.
In the process of using the gaseous fluorine removing agent to remove fluorine, the invention can realize the control of the fluorine removing process by controlling the concentration of the gaseous fluorine removing agent, the adding speed of the gaseous fluorine removing agent and the like. Meanwhile, a gaseous fluorine removing agent is continuously blown into the solution, and the gaseous fluorine removing agent can react with fluorine in the solution to precipitate the fluorine; in addition, by utilizing the property that gaseous mixed chlorinating agent enters the solution and is rapidly released heat when being hydrolyzed when meeting water, partial defluorinating agent forms colloidal defluorinating agent with extremely fine particles and high surface activity in the fluorine-containing solution so as to further remove fluorine in the solution. In addition, because the gas and the liquid can be fully mixed, the gas can be introduced to play a role in stirring, so that the explosive hydrolysis nucleation generation of the adsorbent with the high specific surface area can be realized, the adsorbent can immediately adsorb fluorine in the solution, the adsorbent for adsorbing fluorine can be used as a crystal nucleus for chloride hydrolysis to generate a fresh adsorbent, the fluorine is continuously adsorbed, and the adsorption capacity of the adsorbent is greatly improved. Particularly, the adoption of the formula of the mixed gaseous chloride can greatly improve the removal efficiency of fluorine in the solution. In conclusion, the fluorine in the fluorine-containing solution can be accurately and efficiently removed.
Compared with the prior art, the invention has the beneficial effects that:
1. the method has the advantages of simple operation of the defluorination process, short flow, easy control of the process, low cost and easy operation; taking the fluorine-containing solution generated in the waste battery recovery process as an example, after the fluorine-removing reagent is used for treatment, the removal rate of fluorine in the solution reaches more than 90 percent.
2. The gaseous defluorinating agent is the combination of more than two of the gaseous chlorides such as titanium tetrachloride, silicon tetrachloride, cesium chloride, stannic chloride, aluminum chloride, bismuth chloride, ferric chloride and the like, and has the advantages of simple component composition, low cost, environmental friendliness, simple and easy defluorination process and good defluorination effect.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of the composition of the gaseous fluorine removal agent of the present invention and the process flow for its use.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Table 1 shows the content of each element in the black powder of the waste power battery collected from different places, and the composition of the leachate obtained by wet leaching the black powder is shown in table 2 as the raw material of the example.
Table 1 anode and cathode mixed powders (mass fraction,%) obtained by disassembling and sorting waste batteries from different sources
TABLE 2 ingredients (g/L) of leachate obtained by wet leaching of Black flour #1 and Black flour #2
Example 1:
a gaseous defluorinating agent is prepared from gaseous titanium tetrachloride and gaseous silicon tetrachloride by respectively mixing 20% and 80% of the total mass.
The method for removing fluorine from the solution by using the gaseous fluorine removing agent (removing fluorine from black powder # 1-leaching solution) as shown in figure 1 comprises the following steps:
(1) Taking 2L of black powder # 1-leaching solution, and adjusting the pH value to 7;
(2) Diluting a gaseous defluorinating agent by using nitrogen to obtain a diluted gaseous defluorinating agent with the mass concentration of 60.49%, introducing 10mL/min of the diluted gaseous defluorinating agent into each liter of solution, controlling the defluorination reaction temperature to be 80 ℃, the defluorination reaction time to be 100 min, maintaining the pH value of the solution to be between 6 and 7 by using sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to enable the concentration of the polyacrylamide to be 10mg/L, standing for a period of time, and filtering to obtain defluorination residues and the defluorination solution.
And analyzing the fluorine content of the solution after fluorine removal, and calculating to obtain the fluorine removal rate of 90.58%.
Example 2:
a gaseous defluorinating agent is prepared from gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous stannic chloride and gaseous aluminum chloride by respectively mixing the components in percentage by mass of 50%, 20%, 10% and 10%.
The method for removing fluorine from the solution by using the gaseous fluorine removing agent (removing fluorine from black powder # 1-leaching solution) as shown in figure 1 comprises the following steps:
(1) 2L of black powder # 1-leaching solution is taken, and the pH value is adjusted to 7;
(2) Diluting a gaseous defluorinating agent by using argon to obtain a diluted gaseous defluorinating agent with the mass concentration of 30.49%, introducing 20mL/min of the diluted gaseous defluorinating agent into each liter of solution, controlling the defluorination reaction temperature to be 75 ℃, the defluorination reaction time to be 180 min, maintaining the pH value of the solution to be between 5 and 7 by using sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to ensure that the concentration of the polyacrylamide is 5mg/L, standing for a period of time, and filtering to obtain defluorination residues and the defluorination solution.
And (3) analyzing the fluorine content of the solution after fluorine removal, and calculating to obtain the fluorine removal rate of 98.01%.
Example 3:
a gaseous defluorinating agent is prepared from gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous tin tetrachloride and gaseous aluminum chloride by the weight percentages of 50%, 70%, 10% and 20%, respectively.
The method for removing fluorine from the solution by using the gaseous fluorine removing agent (removing fluorine from black powder # 2-leaching solution) as shown in figure 1 comprises the following steps:
(1) 2L of black powder # 2-leaching solution is taken, and the pH value is adjusted to 8;
(2) Diluting a gaseous defluorinating agent by adopting argon to obtain a diluted gaseous defluorinating agent with the mass concentration of the gaseous defluorinating agent of 60 percent, introducing 5mL/min of the diluted gaseous defluorinating agent into each liter of solution, controlling the defluorination reaction temperature to be 90 ℃, controlling the defluorination reaction time to be 240min, maintaining the pH value of the solution to be between 4 and 7 by adopting sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to enable the concentration of the polyacrylamide to be 5mg/L, standing for a period of time, filtering to obtain defluorination residues and a defluorination solution, analyzing the fluorine content of the defluorination solution, and calculating to obtain the fluorine removal rate of 96.07%.
Example 4:
the gaseous defluorinating agent is compounded with gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous tin tetrachloride and gaseous aluminum chloride in the weight ratio of 80%, 5% and 10%.
The method for removing fluorine from the solution by using the gaseous fluorine removing agent (removing fluorine from black powder # 2-leaching solution) as shown in figure 1 comprises the following steps:
(1) 2L of black powder # 2-leaching solution is taken, and the pH value is adjusted to 7;
(2) Diluting a gaseous defluorinating agent by using argon to obtain a diluted gaseous defluorinating agent with the mass concentration of 30.49 percent, introducing 10mL/min of the diluted gaseous defluorinating agent into each liter of solution, controlling the defluorination reaction temperature to be 90 ℃, controlling the defluorination reaction time to be 220 min, maintaining the pH value of the solution to be between 5 and 7 by using sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to ensure that the concentration of the polyacrylamide is 5mg/L, standing for a period of time, and filtering to obtain defluorination residues and the defluorination solution.
And analyzing the fluorine content of the solution after fluorine removal, and calculating to obtain the fluorine removal rate of 95.75%.
Example 5:
a gaseous defluorinating agent is prepared from gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous stannic chloride and gaseous aluminum chloride by respectively mixing the components in percentage by mass of 20%, 10% and 10%.
The method for removing fluorine from the solution by using the gaseous fluorine removing agent (removing fluorine from black powder # 2-leaching solution) as shown in figure 1 comprises the following steps:
(1) 2L of black powder # 2-leaching solution is taken, and the pH value is adjusted to 7;
(2) Diluting a gaseous defluorinating agent by using argon to obtain a diluted gaseous defluorinating agent with the mass concentration of 30.49%, introducing 10mL/min of the diluted gaseous defluorinating agent into each liter of solution, controlling the defluorination reaction temperature to be 90 ℃, the defluorination reaction time to be 220 min, maintaining the pH value of the solution to be between 5 and 7 by using sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to ensure that the concentration of the polyacrylamide is 5mg/L, standing for a period of time, and filtering to obtain defluorination residues and a defluorination solution.
And analyzing the fluorine content of the solution after fluorine removal, and calculating to obtain the fluorine removal rate of 94.06%.
Comparative example 1:
this example is a comparative example, and is primarily illustrative, and it has been reported that a single or non-gaseous chloride is used as a gaseous defluorinating agent, unlike the present invention. A comparative example comprising the steps of:
(1) 2L of black powder # 1-leaching solution is taken, and the pH value is adjusted to 7;
(2) Adding 4.5 g of titanium dioxide into each liter of solution, controlling the defluorination reaction temperature to be 80 ℃, controlling the defluorination reaction time to be 100 min, maintaining the pH value of the solution to be between 6 and 7 by adopting sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to ensure that the concentration of the polyacrylamide is 10mg/L, standing for a period of time, and filtering to obtain defluorination residues and a defluorination solution.
Fluorine content analysis is carried out on the solution after fluorine removal, and the fluorine removal rate is calculated to be 39.74%.
Comparative example 2:
this example is a comparative example, and is primarily intended to illustrate the differences between the use of a single or non-gaseous chloride as a gaseous defluorinating agent and the present invention. A comparative example comprising the steps of:
(1) 2L of black powder # 1-leaching solution is taken, and the pH value is adjusted to 7;
(2) Adding 4.5 g of solid aluminum chloride into each liter of solution, controlling the defluorination reaction temperature to be 80 ℃, controlling the defluorination reaction time to be 100 min, maintaining the pH value of the solution to be between 6 and 7 by adopting sodium hydroxide or sulfuric acid in the defluorination process, and stirring the solution in the defluorination process;
(3) And after the defluorination reaction is finished, adding polyacrylamide into the solution to enable the concentration of the polyacrylamide to be 10mg/L, standing for a period of time, and filtering to obtain defluorination residues and the defluorination solution.
Fluorine content analysis is carried out on the solution after fluorine removal, and the fluorine removal rate is calculated to be 71.29%.
In conclusion, the invention adopts the combination of more than two arbitrary gaseous chlorides as the gaseous defluorinating agent, and has the advantages of simple component composition, low cost, environmental protection, simple and easy defluorination process and good defluorination effect. The defluorination process is simple to operate, short in flow, easy to control, low in cost and easy to operate; taking the fluorine-containing solution generated in the waste battery recovery process as an example, after the fluorine-removing reagent is used for treatment, the removal rate of fluorine in the solution reaches more than 90 percent.
Claims (9)
1. A method for removing fluorine from a solution by using a gaseous fluorine removing agent, which is characterized by comprising the following steps:
(1) Adjusting the pH value of the solution to be defluorinated to be more than 2;
(2) Diluting and fully mixing the gaseous defluorinating agent by using inert gas, and introducing the diluted gaseous defluorinating agent into a solution to be defluorinated for defluorination; the gaseous defluorinating agent is gaseous chloride, and the gaseous chloride is the combination of any two or more of titanium tetrachloride, silicon tetrachloride, cesium chloride, stannic chloride, aluminum chloride, bismuth chloride and ferric chloride;
(3) And after the defluorination reaction is finished, adding a flocculating agent for precipitation, and filtering the solution to obtain defluorination residues and a defluorination solution.
2. The method for removing fluorine from a solution by using a gaseous fluorine removal agent as claimed in claim 1, wherein in the step (1), the solution to be subjected to fluorine removal is a fluorine-containing solution generated in a wet recovery process of the waste power battery, and the fluorine-containing solution contains Li 1 to 5g/L and F0.2 to 0.8g/L.
3. The method for removing fluorine from a solution by using a gaseous fluorine removing agent as claimed in claim 1, wherein in the step (1), the pH value of the solution to be subjected to fluorine removal is adjusted to 7 to 8.
4. The method for removing fluorine from a solution by using a gaseous fluorine removing agent according to claim 1, wherein in the step (2), when the gaseous fluorine removing agent is diluted by using an inert gas, the mass of the gaseous fluorine removing agent is controlled to be more than 20% of the total mass of the gas, and the inert gas is any one or a combination of more of argon and nitrogen.
5. The method for removing fluorine from a solution by using a gaseous fluorine removing agent according to claim 1, wherein in the step (2), when the diluted gaseous fluorine removing agent is introduced into the solution to be subjected to fluorine removal, the introduction amount of the diluted gaseous fluorine removing agent is controlled according to the introduction amount of the diluted gaseous fluorine removing agent per liter of the solution of 2 to 80mL/min, the temperature of the fluorine removal reaction is controlled to be 60 to 95 ℃, and the time of the fluorine removal reaction is controlled to be 30 to 240min.
6. The method for removing fluorine in solution by using gaseous fluorine removing agent as claimed in claim 5, wherein in the step (2), sodium hydroxide or sulfuric acid is used for adjusting the pH value of the solution during the fluorine removing reaction, and the pH value of the solution is maintained to be more than 2.5.
7. The method for removing fluorine from a solution by using a gaseous fluorine removing agent according to any one of claims 1 to 6, wherein in the step (3), the flocculating agent comprises any one or a combination of more of polyacrylamide, polyacrylic acid, sodium polyacrylate and calcium polyacrylate, and the addition amount of the flocculating agent is 5-25 mg/L.
8. A gaseous fluorine removal agent for the method according to any one of claims 1 to 7, wherein the gaseous chloride is a combination of any two or more of titanium tetrachloride, silicon tetrachloride, tin tetrachloride and aluminum chloride.
9. The gaseous fluorine removing agent according to claim 8, wherein the gaseous fluorine removing agent comprises gaseous titanium tetrachloride, gaseous silicon tetrachloride, gaseous tin tetrachloride and gaseous aluminum chloride according to a mass ratio of 10 to 80: 5 to 90: 0 to 25: 0 to 40.
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| TW495487B (en) * | 1999-06-07 | 2002-07-21 | Ind Tech Res Inst | Process for removing fluoride from wastewater |
| CN104496063A (en) * | 2014-11-17 | 2015-04-08 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for removing fluorine in wastewater |
| CN107538706A (en) * | 2017-10-12 | 2018-01-05 | 威海新元化工有限公司 | A kind of system and method that volatile matter in fluorine-silicon compounded rubber stock is removed using inert gas |
| CN111302465B (en) * | 2020-03-09 | 2022-05-31 | 山东环瑞生态科技有限公司 | Novel liquid defluorination medicament and preparation method and application thereof |
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