CN112850867A - Deep defluorination medicament and preparation method thereof - Google Patents
Deep defluorination medicament and preparation method thereof 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/58—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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses a deep defluorination medicament and a preparation method thereof, belonging to the technical field of chemical materials. The following technical scheme is specifically disclosed: comprises the following raw materials in parts by weight: 20-30% of calcium salt, 3-5% of acid, 10-15% of iron salt, 10-15% of aluminum salt, 2-3% of magnesium salt, 2-3% of water glass and the balance of water; the ferric salt is nano ferric silicate; meanwhile, the invention defines the preparation method of the nano iron silicate and the defluorination medicament. The nano-scale ferric silicate used in the invention has larger specific surface area and can well contact with fluoride ions, thereby increasing the removal efficiency of the product of the invention to the fluoride ions in the wastewater. And secondly, the raw material preparation method is simple and easy to operate, and is convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a deep defluorination medicament and a preparation method thereof.
Background
Fluorine is one of trace elements required by a human body to maintain normal physiological activities, and the fluorine required by the human body is mainly from drinking water. However, if people drink water with over-standard fluorine content for a long time, fluorine poisoning can be generated, and a series of diseases such as dental fluorosis and fluoroostenosis are caused, so that the fluorine content in domestic drinking water is regulated to be 0.5-1.0 mg/L in China, and the fluorine content in discharged water is strictly controlled.
In the prior art, the method for removing fluorine from wastewater mainly comprises a calcium salt precipitation method, an aluminum salt flocculation method, a fluidized bed induced crystallization method, an electrolytic flocculation method, an electrodialysis method, a reverse osmosis method and an absorption methodThe attached method, etc. The calcium salt precipitation method is the most widely applied defluorination method at present, and has the characteristics of simple operation method, convenient treatment, low cost and the like, but the calcium salt precipitation method can only reduce the fluoride ions in the wastewater to 10-20 mg/L. In addition, the aluminum salt flocculation method is carried out by Al3+Formation of Al (OH)3And F-Removal of F by ligand exchange, physical adsorption, entrapment-The method has the advantages of small dosage of medicament, large treatment capacity and the like, but the fluoride content of the treated wastewater is still high. In addition, the fluidized bed induced crystallization method utilizes a solid crystal nucleus growth technology to precipitate and grow fluoride on crystal nuclei so as to achieve the aim of removing the fluoride, the precipitated sludge formed by the method has low water content and high purity, other ions are not introduced into the wastewater, but the treatment process is complex, and the crystal nuclei need to be periodically discharged and supplemented. In addition, the electrodialysis method has advantages of high efficiency of removing fluorine and stable treatment, but the price of the expensive reverse osmosis membrane limits its application. The adsorption method is a method for treating wastewater containing low-concentration fluoride, which is widely applied at present, has mild use conditions and wide raw material sources, does not introduce other ions into the wastewater, but has low adsorption capacity of the adsorbent, and needs to consider the problem of frequent replacement of the adsorbent.
Therefore, it is an urgent need to solve the problem of providing a fluorine removal agent with low cost and high fluorine removal efficiency.
Disclosure of Invention
In view of the above, the present invention provides a fluorine removal agent with low cost, convenient use and high fluorine removal efficiency and a preparation method thereof,
in order to achieve the purpose, the invention adopts the following technical scheme:
the deep fluorine removal agent is characterized by comprising the following raw materials in parts by weight: 20-30% of calcium salt, 3-5% of acid, 10-15% of iron salt, 10-15% of aluminum salt, 2-3% of magnesium salt, 2-3% of water glass and the balance of water;
the iron salt is nano-ferric silicate.
Preferably, the preparation method of the nano iron silicate comprises the following steps:
under the condition of room temperature, uniformly mixing solid raw materials of ferrous sulfate monohydrate and sodium silicate, adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, stirring and reacting, continuously raising the reaction temperature along with the generation of NO by heat emitted in the reaction process, accelerating the reaction, wherein the reaction time is 24-48 hours, the reaction temperature is 0-90 ℃, so that the oxidation and polymerization reactions generated among the raw materials are completed, after the reaction is completed, separating and crushing a solid product, and standing the product for 24-48 hours to obtain the nano ferric silicate.
Has the advantages that: the oxidation reaction mainly comprises the oxidation of ferrous iron into ferric iron; the polymerization reaction is a polymerization reaction that forms polymerized iron silicate.
The nanometer ferric silicate polymer has relatively great specific surface area and is also one kind of polymer flocculant capable of forming precipitate through flocculation with fluoride to form complex. In addition, the water glass has the functions of flocculation, colloid removal and precipitation, and can separate the formed fluoride flocculation precipitation and water separation. Secondly, the purpose of the invention is to make the generated NO or other volatile substances thoroughly overflow, so that the property of the product is stable. On the other hand, the product is crushed to generate temperature, and is placed for a period of time to be cooled.
The iron salt in the invention is selected from nano-scale ferric silicate, has larger specific surface area compared with the common ferric silicate, and can better contact with fluoride ions so as to increase the removal efficiency of the fluoride ions.
Preferably, the acid comprises one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
Has the advantages that: the acid in the invention plays a role in adjusting the pH value of the reaction system. And can prevent partial raw materials from forming precipitate and ensure the stability of the mixture in the system.
Preferably, the calcium salt comprises one or more of calcium chloride, calcium citrate and calcium acetate.
Preferably, the aluminum salt comprises polyaluminum chloride.
Has the advantages that: the polyaluminium chloride has the performances of adsorption, condensation, precipitation and the like, and has the advantages of good stability of spray drying, wide adaptive water range, high hydrolysis speed, strong adsorption capacity, large formed alumen ustum, high density and precipitation speed, low effluent turbidity, good dehydration performance and the like. The calcium salt and the aluminum salt can form stable compound precipitation with fluorine ions so as to achieve the aim of removing the fluorine ions.
Preferably, the magnesium salt comprises one or more of magnesium chloride, magnesium sulfate, magnesium acetate and magnesium citrate.
Has the advantages that: the magnesium salt has the main function of preventing the defluorinating agent of the invention from deliquescing in the process of preservation and ensuring the stability of the effective components of the agent.
Preferably, the ratio of ferrous sulfate monohydrate: sodium silicate: nitric acid: the molar ratio of the sulfuric acid is 1 to (0.017-0.114) to (0.330-0.413) to (1.349-1.478);
has the advantages that: according to the invention, sodium silicate: nitric acid: the molar ratio of the sulfuric acid is 1 to (0.017-0.114) to (0.330-0.413) to (1.349-1.478), so that the performance of the generated nano iron silicate can be ensured to be optimal.
The preparation method of the deep defluorination agent comprises the following steps:
s1: sequentially dissolving calcium salt, iron salt, aluminum salt and magnesium salt in 1/3-1/2 of total water amount at 40-60 ℃ to obtain a mixed solution A;
s2: dissolving water glass in the rest water to obtain solution B;
s3: dropwise adding the solution B into the mixed solution A while stirring, and keeping the temperature of 60 ℃ after dropwise adding to be uniformly stirred to obtain a mixed solution C;
s4: the pH of the mixed solution C was adjusted to 2 to 3 with an acid at room temperature, and then the mixed solution was dried and ground to obtain a defluorinating agent.
Has the advantages that: the deep defluorinating agent provided by the invention combines the nanometer iron silicate with a large specific surface area with calcium salt, iron salt, aluminum salt and magnesium salt, so that the fluoride removal capability is improved. Calcium salt, iron salt, aluminum salt and magnesium salt are dissolved in water to solve the problem of uneven mixing caused by agglomeration, agglomeration and the like of raw materials in the mixing process. The fluoride removing effect of aluminum salt and calcium salt and the synergistic effect of iron salt and magnesium salt are fully exerted. And the water glass is dissolved in water and added into the mixed solution A, so that the mixture can be ensured to fully react in a liquid environment. In the present discovery, the pH of the mixed solution is adjusted to 2 to 3, so as to avoid precipitation of the mixture in the system and reduce the reaction efficiency. The fluorine removing agent prepared by the invention not only utilizes a chemical precipitation method, but also utilizes the complexation formed by the reaction between aluminum salt, water glass and fluorine ions in the fluorine removing process, thereby greatly improving the removal effect on the fluorine ions.
Preferably, the stirring speed in step S3 is 200-300r/min, and the stirring time is 30 min.
Preferably, the pH of the mixed solution C is adjusted in step S4 by using an acid, and the acid includes any one of hydrochloric acid, sulfuric acid and nitric acid.
Has the advantages that: the reaction speed is controlled by controlling the stirring speed and the stirring time, so that the synthesis quality of the medicament is controlled. The stirring speed is controlled to be 200-300r/min, so that not only can the mixture be fully stirred, but also the influence of high shear strength generated by overhigh stirring speed on the reaction can be avoided. The preparation method has the advantages of cheap and easily obtained reagents, simple experimental equipment, convenient operation of the preparation process, mild reaction conditions and suitability for industrial production.
According to the technical scheme, compared with the prior art, the invention discloses the deep fluorine removal agent and the preparation method thereof. And secondly, the raw material preparation method is simple and easy to operate, and is convenient for industrial production.
Drawings
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 described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a deep fluorine removal medicament, which comprises the following raw materials in parts by weight: 20-30% of calcium salt, 3-5% of acid, 10-15% of iron salt, 10-15% of aluminum salt, 2-3% of magnesium salt, 2-3% of water glass and the balance of water;
the iron salt is nano-ferric silicate, and the preparation method comprises the following steps:
under the condition of room temperature, uniformly mixing ferrous sulfate monohydrate and sodium silicate, adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, stirring for reaction, reacting the raw materials at the temperature of 0-90 ℃ for 24-48h, taking out and crushing a product after the reaction is completed, and standing the product for 24-48h to obtain the nano ferric silicate.
In order to further optimize the technical scheme, the acid comprises one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
Further, the calcium salt comprises one or more of calcium chloride, calcium citrate and calcium acetate.
Further, the aluminum salt includes polyaluminum chloride.
Further, the magnesium salt comprises one or more of magnesium chloride, magnesium sulfate, magnesium acetate and magnesium citrate.
Furthermore, the molar ratio of the ferrous sulfate monohydrate to the sodium silicate to the nitric acid to the sulfuric acid is 1: 0.017-0.114: 0.330-0.413: 1.349-1.478.
The embodiment of the invention also provides a preparation method of the deep defluorination medicament, which comprises the following steps:
s1: sequentially dissolving calcium salt, iron salt, aluminum salt and magnesium salt in 1/3-1/2 of total water amount at 40-60 ℃ to obtain a mixed solution A;
s2: dissolving water glass in the rest water to obtain solution B;
s3: dropwise adding the solution B into the mixed solution A while stirring, and keeping the temperature of 60 ℃ after dropwise adding to be uniformly stirred to obtain a mixed solution C;
s4: the pH of the mixed solution C was adjusted to 2 to 3 with an acid at room temperature, and then the mixed solution was dried and ground to obtain a defluorinating agent.
Further, in step S3, the stirring speed is 200-300r/min, and the stirring time is 30 min.
Further, the pH of the mixed solution C is adjusted by using an acid in step S4, where the acid includes any one of hydrochloric acid, nitric acid, and sulfuric acid.
The technical solution of the present invention is further explained by the following embodiments.
Example 1:
the preparation method of the novel defluorination medicament comprises the following steps:
s1: preparing nano iron silicate: under the condition of room temperature, uniformly mixing and stirring solid raw materials of ferrous sulfate monohydrate and sodium silicate according to the molar ratio of 1: 0.017, and then adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, wherein the weight ratio of the ferrous sulfate monohydrate: nitric acid: the molar ratio of the sulfuric acid is 1: 0.330: 1.349, the raw materials are stirred for reaction, the reaction temperature is continuously raised by the heat released in the reaction process and the generation of NO is accompanied, the reaction is accelerated, the reaction time is 24 hours, the reaction temperature is controlled to be 0-90 ℃, so that the oxidation and polymerization reactions generated among the raw materials are completed, and after the reaction is completed, the reactant is taken out and crushed, and is placed for 24-48 hours, so that the nano iron silicate is obtained.
S2: dissolving 21 parts by mass of calcium citrate, 12 parts by mass of nano-iron silicate, 15 parts by mass of polyaluminium chloride and 12 parts by mass of magnesium citrate in 20 parts by mass of water, adding the mixture into a reaction kettle, heating the mixture to 60 ℃, stirring the mixture, and completely dissolving the mixture to obtain a mixed solution A;
s3: dissolving 3 parts by mass of water glass in the residual water, completely dissolving to obtain a solution B, dropwise adding the solution B into the mixed solution A while stirring, and stirring for 30min at a stirring speed of 200r/min and at a temperature of 60 ℃ to obtain a mixed solution C;
s4: after complete cooling, the pH value of the mixed solution C is adjusted to 2 by hydrochloric acid;
s5: drying at 20 deg.C under 0.1MPa, and grinding to 80-150 mesh to obtain the target defluorinating agent.
Example 2:
the preparation method of the novel defluorination medicament comprises the following steps:
s1: preparing nano iron silicate: under the condition of room temperature, uniformly mixing and stirring solid raw materials, namely ferrous sulfate monohydrate and sodium silicate according to the molar ratio of 1: 0.062, and then adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, wherein the weight ratio of the ferrous sulfate monohydrate: nitric acid: the molar ratio of the sulfuric acid is 1: 0.371: 1.413, the raw materials are stirred for reaction, the reaction temperature is continuously increased by the heat released in the reaction process and the generation of NO is accompanied, the reaction is accelerated, the reaction time is 35 hours, the reaction temperature is 0-90 ℃, so that the oxidation and polymerization reactions generated among the raw materials are completed, and after the reaction is completed, the reactant is taken out and crushed, and is placed for 24-48 hours, so that the nano iron silicate is obtained.
S2: dissolving 26 parts by mass of calcium chloride, 14 parts by mass of nano-iron silicate, 13 parts by mass of polyaluminium chloride and 11 parts by mass of magnesium chloride in 20 parts by mass of water, adding the mixture into a reaction kettle, heating the mixture to 60 ℃, stirring the mixture, and completely dissolving the mixture to obtain a mixed solution A;
s3: dissolving 3 parts by mass of water glass in the residual water, completely dissolving to obtain a solution B, dropwise adding the solution B into the mixed solution A while stirring, and continuously stirring for 30min at a stirring speed of 250r/min and at a temperature of 60 ℃ to obtain a mixed solution C;
s4: after complete cooling, the pH value of the mixed solution C is adjusted to 2 by nitric acid;
s5: drying at 20 deg.C under 0.1MPa, and grinding to 80-150 mesh to obtain the target defluorinating agent.
Example 3:
a novel defluorination medicament is prepared by the following steps:
s1: preparing nano iron silicate: under the condition of room temperature, uniformly mixing and stirring solid raw materials of ferrous sulfate monohydrate and sodium silicate according to the molar ratio of 1: 0.114), and then adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, wherein the weight ratio of the ferrous sulfate monohydrate: nitric acid: the molar ratio of the sulfuric acid is 1: 0.413: 1.478, the raw materials are stirred for reaction, the reaction temperature is continuously raised by the heat released in the reaction process and is accompanied with the generation of NO, the reaction is accelerated, the reaction time is 48 hours, the reaction temperature is controlled to be 0-90 ℃, so that the oxidation and polymerization reactions generated among the raw materials are completed, and after the reaction is completed, the reactant is taken out and crushed, and is placed for 24-48 hours, so that the nano iron silicate is obtained.
S2: dissolving 27 parts by mass of calcium acetate, 14 parts by mass of nano-iron silicate, 14 parts by mass of polyaluminium chloride, 14 parts by mass of magnesium sulfate and magnesium acetate in any proportion in 20 parts by mass of water, adding the mixture into a reaction kettle, heating to 40 ℃, stirring, and completely dissolving to obtain a mixed solution A;
s3: dissolving 3 parts by mass of water glass in the residual water, completely dissolving to obtain a solution B, dropwise adding the solution B into the mixed solution A while stirring, and continuously stirring for 30min at the stirring speed of 300r/min and the temperature of 60 ℃ to obtain a mixed solution C;
s4: after complete cooling, the pH value of the mixed solution C is adjusted to 2 by using sulfuric acid;
s5: drying at 20 deg.C under 0.1MPa, and grinding to 80-150 mesh to obtain the target defluorinating agent.
Comparative example 1:
a novel defluorination medicament is prepared by the following steps:
s1: dissolving 26 parts by mass of calcium acetate, 14 parts by mass of iron silicate (ordinary iron silicate, untreated), 13 parts by mass of polyaluminum chloride and 11 parts by mass of magnesium acetate in 20 parts by mass of water, adding the mixture into a reaction kettle, heating to 60 ℃, stirring, and completely dissolving to obtain a mixed solution A;
s2: dissolving 3 parts by mass of water glass in the residual water, completely dissolving to obtain a solution B, dropwise adding the solution B into the mixed solution A while stirring, and continuously stirring for 30min at the temperature of 60 ℃ to obtain a mixed solution C;
s3: after complete cooling, the pH value of the mixed solution C is adjusted to 2 by acid;
s4: drying at 20 deg.C under 0.1MPa, and grinding to 80-150 mesh to obtain defluorinating agent. The technical effects are as follows:
in order to verify the effect of the defluorinating agent prepared by the invention on removing fluoride in wastewater, the defluorinating agents of the embodiments 1-3 and the comparative example 1 are used for treating wastewater, the selected wastewater is taken from the desulfurization wastewater of an electrolytic aluminum workshop of an aluminum industry company in Shandong, the content of fluorine ions in the wastewater is 200mg/L, and the pH value is 6.2. Because the waste water content is higher, two-stage defluorination is adopted, the calcium hydroxide treatment is carried out on the waste water in the first-stage defluorination section, calcium ions and fluorine ions are utilized to form calcium fluoride precipitate to remove most of fluorine ions, the defluorination agent is added into the waste water in the second-stage defluorination section, and a large amount of polymerization colloid with positive charges formed after the defluorination agent is dissolved in water and fluorine ions with negative charges are utilized to form stable compound precipitate so as to achieve the purpose of defluorination. The experimental flow chart is shown in fig. 1, and the specific operation steps are as follows:
preparing a solution: preparing a polyacrylamide solution with the mass concentration of 0.1%. Solutions of the fluorine removing agents corresponding to examples 1 to 3 and comparative example 1 were prepared at a mass concentration of 10%, respectively. Preparing a calcium hydroxide aqueous solution with the mass concentration of 10%.
Primary defluorination: adding calcium hydroxide aqueous solution into the water sample while stirring to adjust the pH of the water sample to 10.5, stirring for 1-2min, adding PAM aqueous solution, and continuously stirring until a large alum blossom precipitate is formed. The separated supernatant was divided into 12 equal parts and the fluoride content was measured, and the results are shown in Table 1.
Secondary defluorination: and dividing 12 water samples subjected to primary defluorination into 3 groups, wherein each group comprises 4 wastewater samples to be treated. The fluorine removing agents of examples 1 to 3 and comparative example 1 were added to 3 groups of wastewater at the addition amounts of 1:200, 1:400 and 1:600, respectively. Continuously stirring for 5-10min, and adding 3-5mg/L PAM aqueous solution into the mixed solution. Stirring was continued until large alum flocs were formed, and the mixture was allowed to stand for 2min, and the supernatant was collected and the fluoride content was measured, and the results are shown in Table 1.
TABLE 1 removal of fluoride from desulfurization waste water in electrolytic aluminum workshop by defluorinating agent
As can be seen from the above table 1, most of the fluoride in the wastewater can be removed by the primary fluorine removal section and the calcium hydroxide precipitation method, and the content of the residual fluoride in the wastewater after the primary treatment is measured to be 19 mg/L. After the second stage of adding the defluorination agent, the fluoride in the desulfurization waste water of the electrolytic aluminum workshop can be reduced to below 10mg/L in the examples 1 to 3 and the comparative example 1. With the increase of the dosage of the fluorine removal agent, the fluorine removal agent provided by the embodiment of the invention has the advantage of better reducing fluoride in wastewater, and can stably remove the content of fluoride in the wastewater to below 1 mg/L. Therefore, compared with the common ferric silicate, the nanoscale ferric silicate in the invention can better contact with fluoride ions so as to increase the removal efficiency of the fluoride ions.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The deep fluorine removal agent is characterized by comprising the following raw materials in parts by weight: 20-30% of calcium salt, 3-5% of acid, 10-15% of iron salt, 10-15% of aluminum salt, 2-3% of magnesium salt, 2-3% of water glass and the balance of water;
the iron salt is nano-ferric silicate.
2. The deep fluorine removal agent as claimed in claim 1, wherein the preparation method of the nano iron silicate comprises the following steps:
under the condition of room temperature, uniformly mixing ferrous sulfate monohydrate and sodium silicate, adding a mixed solution of nitric acid with the mass concentration of 98% and sulfuric acid with the mass concentration of 93%, stirring for reaction, reacting at the temperature of 0-90 ℃ for 24-48h, separating and crushing a solid product after the reaction is completed, and standing for 24-48h to obtain the nano ferric silicate.
3. The deep fluorine removal agent as claimed in claim 1, wherein the molar ratio of ferrous sulfate monohydrate, sodium silicate, nitric acid and sulfuric acid is 1: 0.017-0.114: 0.330-0.413: 1.349-1.478.
4. The agent for deep fluorine removal according to claim 1, wherein the acid comprises one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
5. The deep defluorinating agent of claim 1, wherein the calcium salt comprises one or more of calcium chloride, calcium citrate, and calcium acetate.
6. The agent of claim 1, wherein the aluminum salt comprises polyaluminum chloride.
7. The deep fluorine removal agent of claim 1, wherein the magnesium salt comprises one or more of magnesium chloride, magnesium sulfate, magnesium acetate and magnesium citrate.
8. The method for preparing the deep fluorine removal agent according to any one of claims 1 to 7, comprising the following steps:
s1: sequentially dissolving calcium salt, iron salt, aluminum salt and magnesium salt in 1/3-1/2 of total water amount at 40-60 ℃ to obtain a mixed solution A;
s2: dissolving water glass in the rest water to obtain solution B;
s3: dropwise adding the solution B into the mixed solution A while stirring, and keeping the temperature of 60 ℃ after dropwise adding to be uniformly stirred to obtain a mixed solution C;
s4: and (3) adjusting the pH value of the mixed solution C to 2 at room temperature, and then drying and grinding the mixed solution C to obtain the defluorinating agent.
9. The method as claimed in claim 8, wherein the stirring speed in step S3 is 200-300r/min, and the stirring time is 30 min.
10. The method for preparing an agent for deep fluorine removal according to claim 8, wherein the pH of the mixed solution C is adjusted by using an acid in step S4, and the acid comprises any one of hydrochloric acid, sulfuric acid and nitric acid.
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| CN113072152A (en) * | 2021-06-04 | 2021-07-06 | 赛恩斯环保股份有限公司 | Preparation method and application of defluorination and heavy metal removal polynuclear medicament |
| CN113955873A (en) * | 2021-09-23 | 2022-01-21 | 鄂尔多斯市紫荆创新研究院 | Water treatment defluorinating agent suitable for micro-polluted raw water and preparation and use methods thereof |
| CN114477564A (en) * | 2022-03-17 | 2022-05-13 | 中国矿业大学(北京) | Defluorination medicament, preparation method and method for defluorination of hydrofluoric acid wastewater |
| CN114590879A (en) * | 2022-03-17 | 2022-06-07 | 中国矿业大学(北京) | Defluorination agent, preparation method of defluorination agent and method for treating fluorine-containing mine water |
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| CN114477564A (en) * | 2022-03-17 | 2022-05-13 | 中国矿业大学(北京) | Defluorination medicament, preparation method and method for defluorination of hydrofluoric acid wastewater |
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| CN114477564B (en) * | 2022-03-17 | 2023-08-25 | 中国矿业大学(北京) | Defluorination medicament, preparation method and defluorination method for hydrofluoric acid wastewater |
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