CN114210299B - Preparation method of fly ash-based defluorination adsorbent and fly ash-based defluorination adsorbent - Google Patents

Preparation method of fly ash-based defluorination adsorbent and fly ash-based defluorination adsorbent Download PDF

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CN114210299B
CN114210299B CN202111532591.3A CN202111532591A CN114210299B CN 114210299 B CN114210299 B CN 114210299B CN 202111532591 A CN202111532591 A CN 202111532591A CN 114210299 B CN114210299 B CN 114210299B
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fly ash
minutes
adsorbent
acid
modifying reagent
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CN114210299A (en
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包一翔
李井峰
郭强
蒋斌斌
张海琴
唐佳伟
李�杰
***
李俏
何瑞敏
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Guoneng Shendong Coal Group Co Ltd
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Guoneng Shendong Coal Group Co Ltd
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Abstract

The preparation method of the fly ash-based defluorination adsorbent comprises the steps of respectively adding (35-140) 3.7-7 (0.5-4) 0.5-1 (0.5-1) fly ash, a first modifying reagent, a second modifying reagent, a first activating agent, a second activating agent and a stabilizing agent into a ball milling device for ball milling treatment to obtain the fly ash-based defluorination adsorbent; the first modifying agent is a substance having an iron active component and/or an aluminum active component; the second modifying reagent is a functional material with a porous structure and adsorption performance. Also provides a fly ash-based defluorination adsorbent and application thereof. The preparation method adopts a mechanochemical method, replaces the traditional aqueous phase reaction with a solid phase reaction, and converts 100% of raw materials into the modified defluorination adsorbent.

Description

Preparation method of fly ash-based defluorination adsorbent and fly ash-based defluorination adsorbent
Technical Field
The invention belongs to the field of adsorbents, and particularly relates to a preparation method of a fly ash-based defluorination adsorbent and the fly ash-based defluorination adsorbent.
Background
The problem of exceeding the standard of fluoride in water is a common challenge facing the world, and long-term intake of the exceeding fluoride drinking water can cause dental fluorosis, fluoripathy and the like, can inhibit the in-vivo enzyme conversion process, destroy the in-vivo calcium and phosphorus metabolism, lead to calcium deposition in normal tissues, cause unbalance of the proportion of fluorine and phosphorus and cause abnormal metabolism of normal cells. Therefore, fluoride removal is an important topic for ensuring human health and water resource utilization.
Mine water is drainage water generated in the geological resource exploitation process of coal and the like, is an underground water resource in essence, and because the stratum is artificially disturbed, minerals containing fluoride can be dissolved into the mine water, so that the concentration of the fluoride is increased. In the coal exploitation process, about 2 tons of mine water can be generated when 1 ton of coal is exploited, so that the mine water is generated annually in China, most of the mine water is discharged and lost, and the mine water accounts for about 60% of industrial and domestic water gaps in China, and the mine water resource is of great significance. However, the problem of exceeding the standard of fluoride in mine water is one of the challenges restricting the application of the fluoride.
The existing common technologies for removing fluoride in water comprise membrane filtration, alumina adsorption, hydroxyapatite adsorption, resin adsorption, activated carbon adsorption, electrochemical flocculation removal and the like, but the technologies have the problem of high cost, and for a large amount of mine water, the economic cost is difficult to be accepted by enterprises.
The existing preparation method of the fly ash-based defluorination adsorbent mainly adopts a hydrothermal synthesis method, adopts lime, calcium hydroxide, ferric salt, shaddock peel, zirconium oxychloride and the like which have adsorption performance on fluoride ions, and realizes the load modification of active components on the surface of the fly ash by regulating and controlling the environment of a pH modified solution and the like, thereby achieving the adsorption of fluoride. The technology adopts a hydrothermal synthesis method, modification is needed to be completed in an aqueous solution, and subsequent treatment processes such as filtration, precipitation, separation, heating and the like are needed, so that waste residues and waste liquid are generated, the treatment steps are more, and secondary energy consumption is increased in the heating process, so that more environmental burden is caused, and the technology does not accord with the concept of green low-carbon development.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of a fly ash-based defluorination adsorbent, which adopts a mechanochemical method to replace the traditional aqueous phase reaction by solid phase reaction, and converts 100% of the raw materials such as fly ash, modifying reagent, activating agent and the like into the modified defluorination adsorbent;
the second object of the invention is to provide a fly ash-based defluorination adsorbent prepared by the preparation method;
a third object of the present invention is to provide the use of the fly ash-based defluorination adsorbent.
In order to achieve the first object of the present invention, the following technical solutions are adopted:
the preparation method of the fly ash-based defluorination adsorbent comprises the steps of respectively adding 6 raw materials of fly ash, a first modifying reagent, a second modifying reagent, a first activating agent, a second activating agent and a stabilizing agent into a ball milling device for ball milling treatment to obtain the fly ash-based defluorination adsorbent; wherein,,
the weight ratio of the fly ash, the first modifying agent, the second modifying agent, the first activating agent, the second activating agent and the stabilizing agent is (35-140): (3.7-7): (0.5-4): (0.5-1): 1 (0.5-1), such as (35, 50, 65, 80, 105, 120 or 135): 4, 4.5, 5, 5.5, 6 or 6.5): 1, 1.5, 2, 2.5, 3 or 3.5): 0.6, 0.7, 0.8 or 0.9): 1 (0.6, 0.7, 0.8 or 0.9;
the first modifying reagent is a substance with an iron active component and/or an aluminum active component;
the second modifying reagent is a functional material with a porous structure and adsorption performance;
the first activator comprises any one or more of magnesium oxide, calcium sulfate, magnesium sulfate, calcium hydroxide, and magnesium hydroxide;
the second activator comprises any one or a combination of a plurality of saturated sodium silicate aqueous solution, saturated sodium bicarbonate aqueous solution, saturated sodium bisulphite aqueous solution and sodium persulfate aqueous solution;
the stabilizer comprises any one or more of cement, epoxy resin and coagulant (such as calcium formate and calcium aluminate).
Preferably, the raw materials are sequentially added into the ball milling device in stages according to the sequence of the fly ash, the first modifying reagent, the second modifying reagent, the first activator, the second activator and the stabilizer.
Preferably, the preparation method comprises the following steps:
(1) Adding fly ash into a reaction tank of a ball milling device, running for 3-5 minutes (such as 4 minutes) at the rotating speed of 800-1000rpm (such as 850rpm, 900rpm and 950 rpm), thereby reducing the granularity of the fly ash, and applying energy to the fly ash through impact friction between a grinding ball and the grinding ball so as to activate the surface of the fly ash;
(2) Then adding a first modifying reagent into the reaction tank, performing a first-stage reaction, and operating at 500-600rpm (such as 550 rpm) for 2-4 minutes (such as 3 minutes), and then operating at 200-250rpm (such as 210rpm, 220rpm, 230rpm and 240 rpm) for 2-4 minutes (such as 3 minutes);
(3) Then adding a second modifying reagent into the reaction tank, performing a second-stage reaction, running at a rotation speed of 800-1000rpm (such as 850rpm, 900rpm and 950 rpm) for 3-5 minutes (such as 4 minutes), and suspending for 10-15 minutes (such as 12 minutes);
(4) Then adding a first activator to the reaction tank to perform three-stage reaction, and running at a rotation speed of <150rpm (such as 140rpm, 130rpm, 120rpm, 110rpm, 100rpm, 90rpm, 50rpm, 10rpm, etc.) for 5-10 minutes (such as 6 minutes and 8 minutes);
(5) Then adding a second activator into the reaction tank to perform four-stage reaction, and running at the rotating speed of 800-1000rpm (such as 850rpm, 900rpm and 950 rpm) for 2-4 minutes (such as 3 minutes);
(6) And then adding a stabilizer into the reaction tank, performing five-stage reaction, running at the rotating speed of 800-1000rpm (such as 850rpm, 900rpm and 950 rpm) for 3-5 minutes (such as 4 minutes), and standing for more than 60 minutes to obtain the fly ash-based defluorination adsorbent.
According to the preparation method, the grinding balls and the raw materials are subjected to impact friction to generate extremely high instantaneous temperature, the raw materials directly react under the action of the instantaneous temperature, and the reaction activity and the reaction effect are greatly improved, so that the fly ash-based defluorination adsorbent is obtained.
In one embodiment, the first modifying agent comprises a combination of any one or more of ferric oxide, aluminum oxide, ferric oxide, polyaluminum chloride, polyaluminum ferric chloride, polyaluminum sulfate, polyaluminum ferric silicate, high iron polyaluminum chloride, and steel slag.
In one embodiment, the second modifying agent comprises a combination of any one or more of activated carbon, kaolin, montmorillonite, bentonite, attapulgite, and zeolite.
In one embodiment, the second modifying agent is acid pretreated prior to use to increase its use activity; preferably the acid pretreatment is: immersing the second modifying reagent in an acid solution for treatment; preferably the acid solution comprises any one or more of acetic acid, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; preferably the concentration of the acid solution is 15-25wt%, such as 17.5wt%, 20wt% and 22.5wt%; preferably, the treatment temperature of the acid pretreatment is 35-50 ℃, such as 37.5 ℃, 40 ℃, 42.5 ℃, 45 ℃ and 47.5 ℃; the treatment time is 20-40min, such as 25min, 30min and 35min.
In one embodiment, the fly ash is fly ash and/or bottom ash.
The preparation method is applicable to all fly ash, such as fly ash from Beijing Sanhe power plant, shandong Shou Guangdong, ningxia Ning coal power plant and Shanxi Ulmin power plant.
In one embodiment, the ball milling apparatus comprises any one of a planetary ball mill, a tubular ball mill, and a rod ball mill.
In order to achieve the second object of the invention, the invention also provides the fly ash-based defluorination adsorbent prepared by the preparation method.
In order to achieve the third object of the invention, the invention also provides the application of the fly ash-based defluorination adsorbent in mine water defluorination.
The invention has the beneficial effects that:
the preparation method of the fly ash-based defluorination adsorbent adopts a mechanochemical method, replaces the traditional aqueous phase reaction with the solid phase reaction, converts 100% of the raw materials such as the fly ash, the active reagent, the activator and the like into the fly ash-based defluorination adsorbent, avoids the generation of waste liquid and waste residues, has the advantage of successful one-step modification, can be directly used without subsequent treatment, has the concentration of the fly ash dissolved matters lower than the water quality standard of drinking water, has no secondary pollution, and is green and high-efficiency to prepare the fly ash-based defluorination adsorbent.
Detailed Description
The technical scheme and effects of the present invention are further described below with reference to specific embodiments. The following embodiments/examples are only for illustrating the contents of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
The sources of the raw materials and equipment used in the following examples and comparative examples are as follows:
fly ash, fly ash of Shanxi elm upper bay power plant;
the content of the effective substances is 99.9wt percent, the content of the aluminum iron is 36wt percent, and Zhengzhou bamboo clear water treatment materials are available from the company Limited;
alumina, CAS number 17758-78-1, incorporated Europe tolerance materials Co., ltd;
ferrous chloride with a purity of 97wt% and Shanghai national medicine reagent;
the effective content of the polyaluminum chloride is 28 weight percent, and the Shandong Chen reaches chemical industry Co., ltd;
ferroferric oxide with purity of 99.9wt%, manufactured by the company Limited for mineral products of Hui of Chengshou county;
zeolite with a silica content of 69wt% and a density of 2.3g/cm 3 Ningbo Jia and New Material technologies Co., ltd;
activated carbon, 200 mesh, hunan de active carbon Co., ltd;
attapulgite, mineral raw powder, and the source manufacturer of the mineral products in the Zhaoshen county;
calcium sulfate, 99wt% pure, tianjin far chemical agent Co., ltd;
magnesium hydroxide, CAS number 1309-42-8, changzhou Lehuang commercial Co., ltd;
calcium oxide with a purity of 95wt%, new An Jiangyong synthetic plastics factory in Jianshi;
saturated aqueous sodium bisulfite solution, 151g sodium bisulfite is dissolved in 500mL water to prepare saturated aqueous sodium bisulfite solution; the CAS number of the sodium bisulfite is 12-78-16, and is a Hengli chemical industry Co., ltd;
a saturated aqueous sodium silicate solution with a concentration of 36 wt%; the CAS number of the sodium silicate is 13870-30-9, and is a Hengli chemical industry Co., ltd;
calcium aluminate, 52wt%, consolidated Fengrui water purifier material Co., ltd;
cement, cat No. bsn001, albo portland cement;
sodium persulfate with the purity of 97 weight percent is used as a reagent for Shanghai Chinese medicine;
the industrial grade hydroxyapatite defluorinating adsorbent has the purity of 96 weight percent and is manufactured by Simanton biological technology Co., ltd;
ball mill, JC-QM planetary ball mill, qingdao Juchuang environmental protection group Co.
Example 1
The fly ash-based defluorination adsorbent is prepared according to the following preparation method:
mixing and adding the fly ash, the polyaluminum ferric silicate, the zeolite, the calcium sulfate, the saturated sodium bisulphite aqueous solution and the calcium aluminate with the weight ratio of 280:10:2:1:2 into a reaction tank of a ball mill, and performing ball milling treatment for 0.6h at the rotating speed of 600rpm to obtain the fly ash-based defluorination adsorbent A1.
The obtained fly ash-based defluorination adsorbent A1 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L and sulfate ion concentration of 60mg/L, and after the adsorption treatment is carried out for 25 hours, the fluoride removal rate is over 38 percent;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 5% after the same time of the adsorption treatment.
Example 2
The following differences from example 1 are only present:
the raw materials added into the ball mill are fly ash, aluminum oxide, activated carbon, magnesium hydroxide, saturated sodium silicate aqueous solution and cement in a weight ratio of 70:7.5:1:2:2:2; obtaining the fly ash-based defluorination adsorbent A2.
The obtained fly ash-based defluorination adsorbent A2 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L and sulfate ion concentration of 60mg/L, and after the adsorption treatment is carried out for 20 hours, the fluoride removal rate is more than 45%;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 5% after the same time of the adsorption treatment.
Example 3
The following differences from example 1 are only present:
the fly ash, the polyaluminum ferric silicate, the zeolite, the calcium sulfate, the saturated sodium bisulphite aqueous solution and the calcium aluminate which are used as raw materials are sequentially added into a reaction tank of a ball mill for operation in stages in sequence, and each time 1 raw material is added, the ball mill is operated for 3 minutes at the rotating speed of 600 rpm; obtaining the fly ash-based defluorination adsorbent A3.
The obtained fly ash-based defluorination adsorbent A3 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L and sulfate ion concentration of 60mg/L, and after the adsorption treatment is carried out for 15 hours, the fluoride removal rate is more than 50%;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 5% after the same time of the adsorption treatment.
Example 4
The following differences from example 3 are only present:
the zeolite is pretreated by acid; the acid pretreatment process is as follows: the zeolite was immersed in a 20wt% hydrochloric acid solution and treated at 40℃for 30min. Obtaining the fly ash-based defluorination adsorbent A4.
The obtained fly ash-based defluorination adsorbent A4 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L and sulfate ion concentration of 60mg/L, and after the adsorption treatment is carried out for 10 hours, the fluoride removal rate is more than 65%;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 5% after the same time of the adsorption treatment.
Example 5
The same starting materials as in example 4, the preparation process was different:
the fly ash-based defluorination adsorbent is prepared according to the following preparation method:
(1) Adding fly ash into a reaction tank of a ball mill, and running for 3 minutes at the rotating speed of 800 rpm;
(2) Then adding polyaluminum ferric silicate into the reaction tank, performing a first-stage reaction, running for 3 minutes at 600rpm, and then running for 3 minutes at 200 rpm;
(3) Then adding pretreated zeolite into the reaction tank, performing a second-stage reaction, running for 4 minutes at 800rpm, and suspending for 10 minutes;
(4) Then adding calcium sulfate into the reaction tank to perform three-stage reaction, and running for 7 minutes at the rotating speed of 140 rpm;
(5) Then adding saturated sodium bisulphite into the reaction tank to carry out four-stage reaction, and running for 3 minutes at the rotating speed of 800 rpm;
(6) Then adding calcium aluminate into the reaction tank, performing five-stage reaction, running for 3 minutes at the rotating speed of 800rpm, and standing for 65 minutes to obtain the fly ash-based defluorination adsorbent A5.
The obtained fly ash-based defluorination adsorbent A5 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L and sulfate ion concentration of 60mg/L, and after the adsorption treatment is carried out for 2 hours, the fluoride removal rate is more than 70%;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 5% after the same time of the adsorption treatment.
Example 6
The following differences from example 5 are only present:
the raw materials are coal ash, ferrous chloride, polyaluminum chloride, activated carbon, calcium oxide, saturated sodium silicate aqueous solution and cement in a weight ratio of 280:10:4:8:2:2:2;
in the preparation method, the raw materials added in the step (2) are replaced by ferrous chloride and polyaluminium chloride;
the raw materials added in the step (3) are replaced by activated carbon;
the raw materials added in the step (5) are replaced by aluminum cement.
Obtaining the fly ash-based defluorination adsorbent A6.
The obtained fly ash-based defluorination adsorbent A6 is used for adsorbing mine water with fluoride concentration of 4.5mg/L, chloride concentration of 300mg/L, sulfate ion concentration of 60mg/L and turbidity of 50NTU, and after 3.5 hours of adsorption treatment, the fluoride removal rate is over 56 percent;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 4% after the same time of the adsorption treatment.
Example 7
The following differences from example 5 are only:
the raw materials are fly ash, ferrous chloride, polyaluminum ferric silicate, activated carbon pretreated by acetic acid, calcium oxide, saturated sodium silicate aqueous solution and calcium aluminate in a weight ratio of 70:6:1.5:1:1:2:1; wherein,,
the acetic acid pretreatment process of the activated carbon comprises the following steps: soaking the activated carbon in a hydrochloric acid solution with the concentration of 15wt% for 28min at the temperature of 50 ℃;
in the preparation method, the raw materials added in the step (2) are replaced by ferrous chloride and polymeric aluminum ferric silicate;
the raw materials added in the step (3) are replaced by activated carbon pretreated by acetic acid;
the raw materials added in the step (4) are replaced by calcium oxide;
the raw material added in the step (5) is replaced by saturated sodium silicate aqueous solution.
Obtaining the fly ash-based defluorination adsorbent A7.
The obtained fly ash-based defluorination adsorbent A7 is used for adsorbing mine water with fluoride concentration of 6.25mg/L, and after 3 hours of adsorption treatment, the fluoride removal rate is more than 60%;
when the industrial grade hydroxyapatite defluorinating adsorbent is used for carrying out adsorption treatment on the mine water, the fluoride removal rate is less than 10% after the same time of the adsorption treatment.
Example 8
The following differences from example 5 are only:
the raw materials are the fly ash, aluminum oxide, ferroferric oxide, sulfuric acid pretreated attapulgite, magnesium hydroxide, saturated sodium silicate aqueous solution and sodium persulfate with the weight ratio of 100:8:2:1:1:1:1; wherein,,
the sulfuric acid pretreatment process of the attapulgite comprises the following steps: soaking the attapulgite in a sulfuric acid solution with the concentration of 25wt% for 20min at the temperature of 35 ℃;
in the preparation method, the raw materials added in the step (2) are replaced by aluminum oxide and ferroferric oxide;
the raw materials added in the step (3) are replaced by the attapulgite pretreated by sulfuric acid;
the raw materials added in the step (4) are replaced by magnesium hydroxide;
the raw materials added in the step (5) are replaced by saturated sodium silicate aqueous solution;
the raw material added in the step (6) is replaced by sodium persulfate.
Obtaining the fly ash-based defluorination adsorbent A8.
The obtained fly ash-based defluorination adsorbent A8 is used for adsorbing mine water with fluoride concentration of 4.6mg/L, chloride concentration of 210mg/L and sulfate ion concentration of 550mg/L, after the adsorption treatment is carried out for 41 hours, the fluoride removal rate reaches over 40 percent, the sulfate ion removal rate reaches about 80 percent, and the sulfate ion concentration is reduced to 117mg/L;
when the mine water is adsorbed by the industrial hydroxyapatite defluorinating adsorbent, the fluoride removal rate is almost 0% and the sulfate ion removal rate is 10% after the same time of the adsorption treatment.

Claims (12)

1. The preparation method of the fly ash-based defluorination adsorbent is characterized in that 6 raw materials of fly ash, a first modifying reagent, a second modifying reagent, a first activator, a second activator and a stabilizer are respectively added into a ball milling device for ball milling treatment to obtain the fly ash-based defluorination adsorbent; wherein,,
the weight ratio of the fly ash to the first modifying reagent to the second modifying reagent to the first activating agent to the second activating agent to the stabilizing agent is (35-140): 3.7-7): 0.5-4): 0.5-1): 1 (0.5-1);
the first modifying reagent is a substance with an iron active component and/or an aluminum active component;
the second modifying reagent is a functional material with a porous structure and adsorption performance;
the first activator comprises any one or more of magnesium oxide, calcium sulfate, magnesium sulfate, calcium hydroxide, and magnesium hydroxide;
the second activator comprises any one or a combination of a plurality of saturated sodium silicate aqueous solution, saturated sodium bicarbonate aqueous solution, saturated sodium bisulphite aqueous solution and sodium persulfate aqueous solution;
the stabilizer comprises cement and/or calcium aluminate;
the method comprises the following steps:
(1) Adding the fly ash into a reaction tank of a ball milling device, and running for 3-5 minutes at the rotating speed of 800-1000 rpm;
(2) Then adding a first modifying reagent into the reaction tank, performing a first-stage reaction, running at 500-600rpm for 2-4 minutes, and then running at 200-250rpm for 2-4 minutes;
(3) Then adding a second modifying reagent into the reaction tank, performing a second-stage reaction, running for 3-5 minutes at a rotating speed of 800-1000rpm, and suspending for 10-15 minutes;
(4) Then adding a first activator into the reaction tank to perform three-stage reaction, and running at the rotating speed of <150rpm for 5-10 minutes;
(5) Then adding a second activator into the reaction tank to perform four-stage reaction, and running for 2-4 minutes at the rotating speed of 800-1000 rpm;
(6) And then adding a stabilizer into the reaction tank, performing five-stage reaction, running for 3-5 minutes at the rotating speed of 800-1000rpm, and standing for more than 60 minutes to obtain the fly ash-based defluorination adsorbent.
2. The method of claim 1, wherein the first modifying agent comprises any one or more of ferric oxide, aluminum oxide, ferric oxide, polyaluminum chloride, polyaluminum ferric chloride, polyaluminum sulfate, polyaluminum ferric silicate, high iron polyaluminum chloride, and steel slag.
3. The method of claim 1, wherein the second modifying agent comprises a combination of any one or more of activated carbon, kaolin, montmorillonite, bentonite, attapulgite, and zeolite.
4. A method of preparation according to any one of claims 1 to 3, wherein the second modifying agent is acid pretreated prior to use.
5. The method of claim 4, wherein the acid pretreatment is: and immersing the second modifying reagent in an acid solution for treatment.
6. The method of claim 5, wherein the acid solution comprises any one or more of acetic acid, sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
7. The method according to claim 5, wherein the concentration of the acid solution is 15 to 25wt%.
8. The method according to claim 4, wherein the acid pretreatment is carried out at a treatment temperature of 35 to 50℃for a treatment time of 20 to 40 minutes.
9. The method of any one of claims 1-3 and 5-8, wherein the fly ash is fly ash and/or bottom ash.
10. The production method according to claim 9, wherein the ball milling device comprises any one of a planetary ball mill, a tubular ball mill, and a rod ball mill.
11. A fly ash-based defluorinated adsorbent produced by the production process of any one of claims 1 to 10.
12. Use of the fly ash-based defluorination adsorbent of claim 11 for the defluorination of mine waters.
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