CN112316910A - Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group - Google Patents
Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group Download PDFInfo
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Abstract
The method for preparing the adsorbent by sulfonic acid group grafting modification of waste boron mud comprises the following steps: mixing the boron mud after size mixing with diluted hydrochloric acid, stirring, heating and cooling to room temperature, separating filter residues, washing to be neutral, grinding into boron mud acid leaching powder, mixing and dissolving with 3-glycidoxy propyl trimethoxy silane, heating, stirring, refluxing, filtering, washing and drying the filter residues to obtain dried powder; mixing and dissolving with branched chain polyethyleneimine, heating, stirring and refluxing, washing filter residues to be neutral and dried, dissolving and mixing with 2-bromoethane sodium sulfonate uniformly according to a proportion, stirring, heating and refluxing, adding a corresponding amount of dissolved sodium hydroxide, stirring and refluxing, filtering, washing filter residues to be neutral, and drying in vacuum to obtain the group modified boron mud adsorbent. The process realizes the recycling of the solid waste boric sludge, prepares the adsorbent with low cost through specific material design and process optimization, and recycles the magnesium resource in the adsorbent; the sulfonic acid modified boron mud has a more excellent adsorption effect on positively charged pollutants.
Description
The technical field is as follows:
the invention belongs to the technical field of solid waste recycling, and particularly relates to a method for preparing an adsorbent by sulfonic acid group grafting modification of waste boric sludge.
Background art:
boric sludge is a solid waste formed in the production process of boric acid and borax, and seriously pollutes the natural environment and the ecological environment. Boron mud has reached 1700 million tons by 2006 in just Liaoning province and is increasing at a rate of 130 million tons per year, which is very serious. The stacking of the boric sludge not only occupies a large amount of farmlands, but also can alkalize soil near a storage yard, cause migration and transformation of the boric sludge and cause serious pollution to underground water and the like. In addition, the boron mud has fine particles and is easy to fly with wind, thereby causing atmospheric pollution. Therefore, the treatment of the boron mud is not slow.
The adsorption method for removing the pollutants has the advantages of simple and convenient operation, high pollutant removal rate, wide application range and lower cost, and the core of the adsorption method is the adsorbent. At present, a lot of research is focused on the preparation of adsorbents by using porous materials or waste materials with lower cost, so as to achieve the purpose of reducing the cost. The boron mud is prepared into the adsorbent, so that the problem of troublesome boron mud pollution can be solved, and the adsorbent with low cost can be obtained.
In many applications, it is not only required that the adsorbent possess a large surface area and a narrow distribution of pore sizes, but also that the surface of these materials have specific chemical properties. The chemical modification of the adsorbent to improve the catalytic activity and hydrothermal stability of the adsorbent and make it have special physicochemical properties to meet certain specific applications has become a hot topic in the material field. The grafting method, also called post-synthesis method, refers to the post-synthesis modification of the adsorbent prepared by introducing functional group molecules on the surface of the adsorbent.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a method for preparing an adsorbent by sulfonic acid group graft modification of waste boron mud. The method can extract magnesium resource in the boron mud, and silicon in the boron mud is used as a raw material for preparing the adsorbent. The adsorbent modified by grafted sulfonic acid groups has better adsorption effect on pollutants with positive charges, such as heavy metals, cationic dyes and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for preparing the adsorbent by sulfonic acid group grafting modification of waste boric sludge comprises the following steps:
step 1, acid leaching of magnesium:
(1) adding deionized water with equal mass into the boron mud, stirring and mixing to obtain boron mud;
(2) adding hydrochloric acid into deionized water with the same volume, stirring and diluting to obtain diluted hydrochloric acid solution;
(3) according to the mass volume ratio, boron mud: hydrochloric acid 1: (2-6), unit g: mL, adding the diluted hydrochloric acid solution into the boron slurry, stirring and heating, cooling to room temperature, and performing solid-liquid separation to obtain a filtrate and filter residues; wherein the heating temperature is 70-110 ℃, and the heating time is 50-70 min;
step 2, grafting sulfonic acid groups:
(1) washing the filter residue to be neutral, drying and grinding to obtain boric sludge acid leaching powder;
(2) taking 3-glycidoxy propyl trimethoxy silane, and performing acid leaching on boron mud according to the mass-volume ratio: 3-glycidoxypropyltrimethoxysilane 5 (8-11), unit g: adding a solvent, uniformly mixing the three, heating, stirring, refluxing, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃, and the heating time is 22-26 hours;
(3) washing the filter residue with anhydrous ethanol for 3-5 times, and drying to obtain dried powder;
(4) taking branched polyethyleneimine, and drying the powder according to the mass ratio: branched polyethyleneimine ═ 4.5: (3-5), unit g: g, adding a solvent, uniformly mixing the three, heating, stirring, refluxing, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃, and the heating time is 22-26 hours;
(5) washing filter residues to be neutral, drying to obtain a dry solid, taking 2-bromoethane sodium sulfonate, and drying the solid according to the mass ratio: sodium 2-bromoethanesulfonate 5.5: (8-12), unit g: g, adding a solvent, uniformly mixing the three, stirring, heating and refluxing, wherein the heating temperature is 60-80 ℃, and the heating time is 10-14 h;
(6) drying the solid according to mass-volume ratio: sodium hydroxide ═ 5.5: (0.5-1.5), taking sodium hydroxide, dissolving the sodium hydroxide in a solvent, adding the solution into a dry solid stirring system, continuously stirring and refluxing for 10-14h at the same heating temperature to obtain a mixture, filtering to obtain filter residue, repeatedly washing the filter residue to be neutral by deionized water, and performing vacuum drying to obtain a solid product, namely the group modified boron mud adsorbent.
In the step 1(1), the boric sludge comprises 4.47% of Fe, 3.13% of B, 1.43% of Ca, 1.19% of Al, 0.22% of K, 42.81% of Mg and 25.09% of Si by mass percent.
In the step 1(1), boron mud and 1mol/L methylene blue solution are taken, and the mass volume ratio of the boron mud to the methylene blue solution is as follows: methylene blue solution ═ 0.5: 20, unit g: and mL, adding a methylene blue solution into the boron mud, oscillating and adsorbing at the temperature of 30 ℃ and the speed of 200rpm for 40min, wherein the adsorption pH is 8-12, and the adsorption amount of the boron mud to the methylene blue is 253.3224-276.2132mg/g through an ultraviolet spectrophotometer.
In the step 1(3), the stirring speed is 200-500 rpm. The stirring time is 50-70 min.
In the step 1(3), the filtrate is extracted magnesium liquid, and the magnesium content of the extracted magnesium liquid is 31.85-36.15%.
In the step 2(1), the grinding is carried out to a degree of 200 meshes.
In the step 2(2), the stirring speed is 200-400rpm, and the stirring time is 22-26 h.
In the step 2(2), the solvent is absolute ethyl alcohol, and excessive amount is added to ensure that the 3-glycidoxypropyltrimethoxysilane is completely dissolved.
In the step 2(4), the solvent is absolute ethyl alcohol, and an excessive amount is added to ensure that the branched polyethyleneimine is completely dissolved.
In the step 2(4), the stirring speed is 200-400rpm, and the stirring time is 22-26 h.
In the step 2(5), the solvent is deionized water, and an excessive amount is added to ensure that the sodium 2-bromoethane sulfonate is completely dissolved.
In the step 2(5), the stirring speed is 200-400rpm, and the stirring time is 10-14 h.
In the step 2(6), the stirring speed is 200-400rpm, and the stirring time is 10-14 h.
In the step 2(6), the drying temperature is 50-60 ℃ and the time is 10-12 h.
In the step 2(6), the modified boron mud adsorbent and 1mol/L methylene blue solution are taken, and the mass volume ratio of the modified boron mud adsorbent to the methylene blue solution is as follows: methylene blue solution ═ 0.5: 20, unit g: and mL, adding a methylene blue solution into the modified boron mud adsorbent, oscillating and adsorbing at the temperature of 30 ℃ and the speed of 200rpm for 40min, wherein the adsorption pH is 8-12, and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 354.3824-367.5487mg/g through an ultraviolet spectrophotometer.
According to the process, porous silicon dioxide is obtained through acid leaching of boric sludge, and an adsorption basis is provided. The grafted sulfonic acid group after specific modification enables the surface of the adsorbent to be negatively charged so as to realize the specific adsorption effect on positively charged pollutants such as cationic dyes and heavy metal ions, exert the adsorption potential to the maximum extent and avoid pore channel blockage.
The invention has the beneficial effects that:
the technology for preparing the adsorbent by sulfonic acid group grafting modification of the waste boron mud realizes the recycling of the solid waste boron mud, prepares the adsorbent with low cost by specific material design and process optimization, and recycles magnesium resources in the adsorbent; the boric sludge modified by sulfonic acid has more excellent adsorption effect on positively charged pollutants.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
The method for preparing the adsorbent by sulfonic acid group grafting modification of waste boric sludge comprises the following steps:
step 1, acid leaching of magnesium:
(1) adding deionized water with equal mass into boron mud, stirring and mixing to obtain boron mud, wherein the boron mud comprises the components of, by mass, 4.47% of Fe, 3.13% of B, 1.43% of Ca, 1.19% of Al, 0.22% of K, 42.81% of Mg and 25.09% of Si;
taking boron mud and 1mol/L methylene blue solution, wherein the mass volume ratio of the boron mud to the methylene blue solution is as follows: methylene blue solution ═ 0.5: 20, unit g: mL, adding a methylene blue solution into the boron mud, oscillating and adsorbing at the temperature of 30 ℃ and the speed of 200rpm for 40min, wherein the adsorption pH is 8-12, and the adsorption amount of the boron mud to the methylene blue is 253.3224-276.2132mg/g through an ultraviolet spectrophotometer;
(2) adding hydrochloric acid into deionized water with the same volume, stirring and diluting to obtain diluted hydrochloric acid solution;
(3) according to the mass volume ratio, boron mud: hydrochloric acid 1: (2-6), unit g: mL, adding the diluted hydrochloric acid solution into the boron slurry, stirring and heating at the stirring speed of 200-500rpm, stirring for 50-70min, cooling to room temperature, and performing solid-liquid separation to obtain a filtrate and filter residues; wherein the heating temperature is 70-110 ℃, the heating time is 50-70min, the filtrate is extracted magnesium liquid, and the magnesium content of the extracted magnesium liquid is 31.85-36.15%.
Step 2, grafting sulfonic acid groups:
(1) washing filter residues to be neutral, drying and grinding the filter residues to 200 meshes to obtain boric sludge acid leaching powder;
(2) taking 3-glycidoxy propyl trimethoxy silane, and performing acid leaching on boron mud according to the mass-volume ratio: 3-glycidoxypropyltrimethoxysilane 5 (8-11), unit g: adding excessive absolute ethyl alcohol to completely dissolve the 3-glycidoxypropyltrimethoxysilane, uniformly mixing the three, heating, stirring and refluxing at the stirring speed of 200-400rpm for 22-26h, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃ and the heating time is 22-26 h;
(3) washing the filter residue with anhydrous ethanol for 3-5 times, and drying to obtain dried powder;
(4) taking 3-5g branched polyethyleneimine, and drying to obtain powder: branched polyethyleneimine ═ 4.5: (3-5) adding excessive absolute ethyl alcohol to completely dissolve the branched polyethyleneimine, uniformly mixing the three, heating, stirring and refluxing at 400rpm for 200-26 h, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃ and the heating time is 22-26 h;
(5) washing filter residues to be neutral, drying to obtain a dry solid, taking 2-bromoethane sodium sulfonate, and drying the solid according to the mass ratio: sodium 2-bromoethanesulfonate 5.5: (8-12), adding excessive ionized water to completely dissolve the 2-bromoethanesulfonic acid sodium salt, uniformly mixing the three, stirring, heating and refluxing, wherein the stirring speed is 200-400rpm, the stirring time is 10-14h, the heating temperature is 60-80 ℃, and the heating time is 10-14 h;
(6) drying the solid according to the mass ratio: sodium hydroxide ═ 5.5: (0.5-1.5), taking sodium hydroxide, dissolving the sodium hydroxide in a solvent, adding the solution into a dry solid stirring system, continuously stirring at the same heating temperature with the stirring speed of 200-400rpm for 10-14h, refluxing for 10-14h to obtain a mixture, filtering to obtain filter residue, repeatedly cleaning the filter residue to be neutral by deionized water, drying at 50-60 ℃ for 10-12h to obtain a solid product, namely the group modified boron mud adsorbent;
taking a modified boron mud adsorbent and a 1mol/L methylene blue solution, wherein the mass volume ratio of the modified boron mud adsorbent to the methylene blue solution is as follows: methylene blue solution ═ 0.5: 20, unit g: and mL, adding a methylene blue solution into the modified boron mud adsorbent, oscillating and adsorbing at the temperature of 30 ℃ and the speed of 200rpm for 40min, wherein the adsorption pH is 8-12, and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 354.3824-367.5487mg/g through an ultraviolet spectrophotometer.
Example 1
1. Acid leaching of magnesium
20g of boric sludge is taken and put into a 500ml three-neck flask, and 20g of deionized water is added for stirring and size mixing. Then 120ml of hydrochloric acid is taken and added with deionized water with the same volume for dilution, and the diluted hydrochloric acid solution is added into a three-neck flask. The three-necked flask was placed in an oil bath, the temperature was adjusted to 110 ℃, and stirring was performed using an overhead stirrer at a stirring rate of 200 rpm. Stirring for 50min, standing the three-neck flask, cooling to room temperature, filtering the solid-liquid mixture in the flask to obtain a filtrate, namely the extracted magnesium liquid, wherein the mass percentage of magnesium in the magnesium liquid is 36.15%.
2. Grafted sulfonic acid groups
And repeatedly washing the filter residue obtained in the step to be neutral by using deionized water, and drying in a constant-temperature drying box. After grinding the cooled acid sludge, 5g of the acid sludge was put into a 100ml three-necked flask, 10ml of 3-glycidoxypropyltrimethoxysilane and 40ml of absolute ethanol were added, and the mixture was stirred with an overhead stirrer at 200rpm for 24 hours and refluxed. The mixture was filtered, and the residue was repeatedly washed with absolute ethanol and dried overnight in a constant temperature drying oven. 4.5g of the dried solid were taken in a 100ml three-necked flask, 40ml of absolute ethanol and 4g of branched polyethyleneimine were added, and the mixture was stirred with an overhead stirrer at 400rpm for 24 hours and refluxed. The mixture was filtered, and the filter residue was washed repeatedly with deionized water and dried overnight in a constant temperature drying oven. Finally, 5.5g of the dried solid was placed in a 100ml three-necked flask, and 10g of sodium 2-bromoethanesulfonate and 20ml of deionized water were added. The flask was placed in a 70 ℃ water bath, stirred at 200rpm for 12h and refluxed. 1.5g of sodium hydroxide are then dissolved in 5ml of deionized water, stirred further and refluxed for 12 h. Filtering the mixture, repeatedly washing the filter residue with deionized water, and drying in a vacuum furnace at 50 deg.C for 12 h. The obtained solid is the boric sludge adsorbent modified by sulfonic acid groups.
3. Adsorption of cationic dyes
Respectively taking 0.5g of the prepared modified boron mud adsorbent and boron mud, adding the obtained mixture into a conical flask, adding 20ml of 1mol/L methylene blue solution, and performing shaking adsorption at the speed of 200rpm for 40min when the pH value is 10 at the temperature of 30 ℃. The adsorption amount of the boron mud to methylene blue is 276.2132mg/g and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 367.5487mg/g measured by an ultraviolet spectrophotometer.
Example 2
1. Acid leaching of magnesium
20g of boric sludge is taken and put into a 500ml three-neck flask, and 20g of deionized water is added for stirring and size mixing. Then 40ml of hydrochloric acid is taken and added with deionized water with the same volume for dilution, and the diluted hydrochloric acid solution is added into a three-neck flask. The three-necked flask was placed in an oil bath, the temperature was adjusted to 70 ℃, and stirring was performed using an overhead stirrer at a stirring rate of 200 rpm. Stirring for 70min, standing the three-neck flask, cooling to room temperature, filtering the solid-liquid mixture in the flask to obtain the filtrate which is the extracted magnesium liquid, wherein the mass percentage of magnesium in the magnesium liquid is 31.85%.
2. Grafted sulfonic acid groups
And repeatedly washing the filter residue obtained in the step to be neutral by using deionized water, and drying in a constant-temperature drying box. After grinding the cooled acid sludge, 5g of the acid sludge was put into a 100ml three-necked flask, 8ml of 3-glycidoxypropyltrimethoxysilane and 40ml of absolute ethanol were added, and the mixture was stirred with an overhead stirrer at 400rpm for 22 hours and refluxed. The mixture was filtered, and the residue was repeatedly washed with absolute ethanol and dried overnight in a constant temperature drying oven. 4.5g of the dried solid were taken in a 100ml three-necked flask, 40ml of absolute ethanol and 3g of branched polyethyleneimine were added, and the mixture was stirred with an overhead stirrer at 200rpm for 22 hours and refluxed. The mixture was filtered, and the filter residue was washed repeatedly with deionized water and dried overnight in a constant temperature drying oven. Finally, 5.5g of the dried solid was placed in a 100ml three-necked flask, and 8g of sodium 2-bromoethanesulfonate and 20ml of deionized water were added. The flask was placed in a 60 ℃ water bath, stirred at 200rpm for 10h and refluxed. Then 0.5g of sodium hydroxide was dissolved in 5ml of deionized water, stirring was continued and reflux was continued for 10 h. Filtering the mixture, repeatedly washing the filter residue with deionized water, and drying in a vacuum furnace at 60 deg.C for 10 h. The obtained solid is the boric sludge adsorbent modified by sulfonic acid groups.
3. Adsorption of cationic dyes
Respectively taking 0.5g of the prepared modified boron mud adsorbent and boron mud, adding the obtained mixture into a conical flask, adding 20ml of 1mol/L methylene blue solution, and performing shaking adsorption at the speed of 200rpm for 40min when the pH value is 8 at the temperature of 30 ℃. The adsorption amount of the boron mud to methylene blue is 253.3224mg/g and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 354.3824mg/g measured by an ultraviolet spectrophotometer.
Comparative example 2-1
The difference from example 2 is that the acid leaching temperature is 60 ℃, the stirring time is 80min, and the adsorption capacity of the modified boron mud adsorbent is 284.3775 mg/g.
Comparative examples 2 to 2
The difference of the method from the example 2 is that the addition amount of the 3-glycidoxypropyltrimethoxysilane is only 6ml, and the adsorption amount of the modified boron mud adsorbent is 290.7622mg/g through detection;
comparative examples 2 to 3
The difference from example 2 is that the amount of branched polyethyleneimine is only 2g, and the modified boron mud adsorbent has an adsorption amount of 297.5921 mg/g.
Example 3
1. Acid leaching of magnesium
20g of boric sludge is taken and put into a 500ml three-neck flask, and 20g of deionized water is added for stirring and size mixing. Then 80ml of hydrochloric acid is taken and added with deionized water with the same volume for dilution, and the diluted hydrochloric acid solution is added into a three-neck flask. The three-necked flask was placed in an oil bath, the temperature was adjusted to 90 ℃, and stirring was performed using an overhead stirrer at a stirring rate of 400 rpm. Stirring for 60min, standing the three-neck flask, cooling to room temperature, filtering the solid-liquid mixture in the flask to obtain filtrate, namely the extracted magnesium liquid, wherein the mass percentage of magnesium in the magnesium liquid is 34.25%.
2. Grafted sulfonic acid groups
And repeatedly washing the filter residue obtained in the step to be neutral by using deionized water, and drying in a constant-temperature drying box. After grinding the cooled acid sludge, 5g of the acid sludge was put into a 100ml three-necked flask, 11ml of 3-glycidoxypropyltrimethoxysilane and 40ml of absolute ethanol were added, and the mixture was stirred with an overhead stirrer at 300rpm for 26 hours and refluxed. The mixture was filtered, and the residue was repeatedly washed with absolute ethanol and dried overnight in a constant temperature drying oven. 4.5g of the dried solid were taken in a 100ml three-necked flask, 40ml of absolute ethanol and 5g of branched polyethyleneimine were added, and the mixture was stirred with an overhead stirrer at 300rpm for 26 hours and refluxed. The mixture was filtered, and the filter residue was washed repeatedly with deionized water and dried overnight in a constant temperature drying oven. Finally, 5.5g of the dried solid was placed in a 100ml three-necked flask, and 12g of sodium 2-bromoethanesulfonate and 30ml of deionized water were added. The flask was placed in a 80 ℃ water bath, stirred at 300rpm for 14h and refluxed. 1.5g of sodium hydroxide are then dissolved in 5ml of deionized water, stirred further and refluxed for 14 h. Filtering the mixture, repeatedly washing the filter residue with deionized water, and drying in a vacuum furnace at 60 deg.C for 10 h. The obtained solid is the boric sludge adsorbent modified by sulfonic acid groups.
3. Adsorption of cationic dyes
Respectively taking 0.5g of the prepared modified boron mud adsorbent and boron mud, adding the obtained mixture into a conical flask, adding 20ml of 1mol/L methylene blue solution, and performing shaking adsorption at the speed of 200rpm for 40min when the pH value is 12 at 30 ℃. The adsorption amount of the boron mud to methylene blue is 265.8124mg/g and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 360.2574mg/g measured by an ultraviolet spectrophotometer.
Claims (10)
1. The method for preparing the adsorbent by sulfonic acid group graft modification of waste boric sludge is characterized by comprising the following steps of:
step 1, acid leaching of magnesium:
(1) adding deionized water with equal mass into the boron mud, stirring and mixing to obtain boron mud;
(2) adding hydrochloric acid into deionized water with the same volume, stirring and diluting to obtain diluted hydrochloric acid solution;
(3) according to the mass volume ratio, boron mud: hydrochloric acid 1: (2-6), unit g: mL, adding the diluted hydrochloric acid solution into the boron slurry, stirring and heating, cooling to room temperature, and performing solid-liquid separation to obtain a filtrate and filter residues; wherein the heating temperature is 70-110 ℃, and the heating time is 50-70 min;
step 2, grafting sulfonic acid groups:
(1) washing the filter residue to be neutral, drying and grinding to obtain boric sludge acid leaching powder;
(2) taking 3-glycidoxy propyl trimethoxy silane, and performing acid leaching on boron mud according to the mass-volume ratio: 3-glycidoxypropyltrimethoxysilane ═ 5 (8-11), the unit g: adding a solvent, uniformly mixing the three, heating, stirring, refluxing, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃, and the heating time is 22-26 hours;
(3) washing the filter residue with anhydrous ethanol for 3-5 times, and drying to obtain dried powder;
(4) taking branched polyethyleneimine, and drying the powder according to the mass ratio: branched polyethyleneimine ═ 4.5: (3-5), adding a solvent, uniformly mixing the three, heating, stirring, refluxing, and filtering to obtain filter residue and filtrate, wherein the heating temperature is 20-35 ℃, and the heating time is 22-26 hours;
(5) washing filter residues to be neutral, drying to obtain a dry solid, taking 2-bromoethane sodium sulfonate, and drying the solid according to the mass ratio: sodium 2-bromoethanesulfonate 5.5: (8-12), adding a solvent, uniformly mixing the three, stirring, heating and refluxing, wherein the heating temperature is 60-80 ℃, and the heating time is 10-14 h;
(6) drying the solid according to mass-volume ratio: sodium hydroxide ═ 5.5: (0.5-1.5), taking sodium hydroxide, dissolving the sodium hydroxide in a solvent, adding the solution into a dry solid stirring system, continuously stirring and refluxing for 10-14h at the same heating temperature to obtain a mixture, filtering to obtain filter residue, washing the filter residue to be neutral, and drying in vacuum to obtain a solid product, namely the group modified boron mud adsorbent.
2. The method for preparing the adsorbent by sulfonic acid group graft modification of the waste boron sludge as claimed in claim 1, wherein in the step 1(1), the boron sludge comprises the components with the mass percentage of 4.47% of Fe, 3.13% of B, 1.43% of Ca, 1.19% of Al, 0.22% of K, 42.81% of Mg and 25.09% of Si.
3. The method for preparing the adsorbent by sulfonic acid group grafting modification of the waste boron sludge according to claim 1, wherein in the step 1(1), the mass volume ratio of the boron sludge to 1mol/L methylene blue solution is: methylene blue solution ═ 0.5: 20, unit g: and mL, adding a methylene blue solution into the boron mud, oscillating and adsorbing at the temperature of 30 ℃ and the speed of 200rpm for 40min, wherein the adsorption pH is 8-12, and the adsorption amount of the boron mud to the methylene blue is 253.3224-276.2132 mg/g.
4. The method for preparing adsorbent by sulfonic acid group graft modification of waste boron sludge as claimed in claim 1, wherein in step 1(3), the stirring speed is 200-500rpm, the stirring time is 50-70min, the filtrate is extracted magnesium solution, and the magnesium content of the extracted magnesium solution is 31.85-36.15%.
5. The method for preparing the adsorbent by sulfonic acid group grafting modification of the waste boron sludge according to claim 1, wherein in the step 2(1), the filter residue is washed and then ground to 200 meshes.
6. The method for preparing adsorbent by sulfonic acid group graft modification of waste boron sludge as claimed in claim 1, wherein in step 2(2), the stirring speed is 200-400rpm, the stirring time is 22-26h, and the solvent is absolute ethanol.
7. The method for preparing adsorbent by sulfonic acid group graft modification of waste boron sludge as claimed in claim 1, wherein in step 2(4), the solvent is absolute ethanol, the stirring speed is 200-400rpm, and the stirring time is 22-26 h.
8. The method for preparing adsorbent by sulfonic acid group graft modification of waste boron sludge as claimed in claim 1, wherein in step 2(5), the solvent is deionized water, the stirring speed is 200-400rpm, and the stirring time is 10-14 h.
9. The method for preparing adsorbent by sulfonic acid group graft modification of waste boron sludge as claimed in claim 1, wherein in step 2(6), the stirring speed is 200-400rpm, the stirring time is 10-14h, the drying temperature is 50-60 ℃, and the drying time is 10-12 h.
10. The method for preparing the adsorbent by sulfonic acid group grafting modification of the waste boron sludge according to claim 1, wherein in the step 2(6), the mass-to-volume ratio of the modified boron sludge adsorbent to 1mol/L of methylene blue solution is as follows: methylene blue solution ═ 0.5: 20, unit g: and mL, adding a methylene blue solution into the modified boron mud adsorbent, oscillating and adsorbing for 2h at the temperature of 30 ℃ and at the speed of 200rpm, wherein the adsorption pH is 8-12, and the adsorption amount of the modified boron mud adsorbent to the methylene blue is 354.3824-367.5487 mg/g.
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