CN109647356B - Preparation method of amphoteric adsorption material and application of amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater - Google Patents

Preparation method of amphoteric adsorption material and application of amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater Download PDF

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CN109647356B
CN109647356B CN201811653751.8A CN201811653751A CN109647356B CN 109647356 B CN109647356 B CN 109647356B CN 201811653751 A CN201811653751 A CN 201811653751A CN 109647356 B CN109647356 B CN 109647356B
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唐裕芳
林天培
艾世杰
李玉芹
周蓉
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Xiangtan University
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Abstract

The invention discloses a preparation method of an amphoteric adsorption material and application of the amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater. The preparation method comprises the steps of condensation polymerization and solidification of the water-soluble lignosulfonate, reaction of the lignosulfonate polycondensate and glycidol trimethyl ammonium chloride and the like. The application of the invention is that the amphoteric adsorption material prepared by modifying lignosulfonate with glycidol trimethyl ammonium chloride is used for adsorbing the anionic dye Congo red and the cationic dye methylene blue in dye wastewater. The adsorbing material obtained by the invention has good adsorbing effect, and the adsorbing capacity is respectively 270.71mg/g and 170.63mg/g when the removal rate of Congo red and methylene blue reaches 90.23% and 56.87%, respectively.

Description

Preparation method of amphoteric adsorption material and application of amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater
Technical Field
The invention relates to preparation of an adsorption material and treatment of dye wastewater, in particular to a preparation method of an amphoteric adsorption material and application of the amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater.
Background
The dye wastewater has complex components and high chroma and CODc, and is one of the industrial wastewater difficult to treat. Although the industrial structure is adjusted in China at present, a batch of dye production enterprises with smaller scale and serious pollution are gradually banned and eliminated. However, in some areas, the number of small dye production enterprises is still large, most of the production processes are backward, and wastewater is directly discharged into a water body without being effectively treated, so that the transparency of the water body is reduced, the dissolved oxygen is deficient, and the growth of aquatic organisms and microorganisms is obviously influenced; meanwhile, the self-cleaning capacity of the water body is reduced, the water body, soil and ecological environment are seriously damaged, and the health of human is harmed.
At present, methods for removing dyes from wastewater roughly include three major types, i.e., physicochemical methods, chemical methods, and biological methods. The adsorption method in the physical and chemical methods is a method which is researched and reported more. The adsorption method is to make the pollutant in the waste water adsorbed on the surface of the porous substance and remove the pollutant by utilizing the physical adsorption and chemical adsorption performance of the powder or the particles of the porous solid. The method is suitable for treating wastewater containing highly toxic substances or substances difficult to biodegrade. Compared with other treatment methods, the adsorption method has the advantages of low cost, easy design, simple equipment, convenient operation, high purification rate, low energy consumption and the like, and is known as an important technology for treating dye wastewater.
Lignosulfonate is one of industrial lignins, and is mainly derived from a spent cooking liquor of sulfite pulping, and various functional groups such as hydroxyl groups and sulfonic acid groups contained in a molecular structure have cation-adsorbing ability, but are not a condition as an adsorbent because of water solubility of lignosulfonate. The invention firstly overcomes the water solubility of the lignosulfonate by an emulsion polymerization method to obtain the water-insoluble lignosulfonate polycondensate. However, the resulting lignosulfonate polycondensate inherently tends to adsorb cations, but has poor performance in adsorbing anions. According to the invention, glycidol trimethyl ammonium chloride is used to modify lignosulfonate polycondensate to obtain the amphoteric adsorbing material capable of adsorbing cations and anions. The preparation method is environment-friendly, efficient, cheap and free of secondary pollution.
Disclosure of Invention
The invention aims to provide a preparation method of an amphoteric adsorption material and application of the amphoteric adsorption material in simultaneous removal of anionic and cationic dyes in wastewater.
The technical scheme of the invention is as follows:
the preparation method of the amphoteric adsorption material is characterized in that the amphoteric adsorption material is prepared by modifying lignosulfonate with glycidol trimethyl ammonium chloride, and specifically comprises the following steps:
(1) sequentially adding formaldehyde, NaOH solution and sodium dodecyl benzene sulfonate into sodium lignosulfonate solution, performing hydroxymethylation under an alkaline condition, adding hydrochloric acid, polymerizing into a water-insoluble sodium lignosulfonate polycondensate under an acidic condition, filtering, washing and drying, wherein the formaldehyde is used as a crosslinking agent, and the sodium dodecyl benzene sulfonate is used as an emulsifier;
(2) suspending the lignosulfonate polycondensate obtained in the step (1) in a mixed solution of N, N Dimethylacetamide (DMA) and NaOH, uniformly stirring, adding glycidol trimethyl ammonium chloride into the uniformly stirred suspension for reaction, and then filtering, washing and drying to obtain the amphoteric adsorbing material capable of adsorbing anions and cations simultaneously.
Further, in the step (1), the concentration of the sodium lignosulfonate solution is 50-200 mg/L, preferably 80-150 mg/L, and more preferably 80-120 mg/L; the concentration of the NaOH solution is 0.5-2 mol/L, preferably 0.7-1.4 mol/L, and more preferably 0.9-1.1 mol/L; the using amount ratio of the sodium lignosulfonate solution to the NaOH solution to the formaldehyde to the sodium dodecyl benzene sulfonate is 150-250 ml, 0.5-5 ml, 15-60 ml, 0.1-2 g, preferably 170-230 ml, 1-3 ml, 25-50 ml, 0.3-1 g, more preferably 180-220 ml, 1-3 ml, 35-45 ml and 0.4-0.7 g.
Further, in the step (1), the hydroxylation reaction is carried out under the stirring condition, the temperature is 60-80 ℃, and the time is 2-3.5 hours; adjusting the pH value of the mixed solution to 2-3 by hydrochloric acid, wherein the temperature of the polymerization reaction is 85-95 ℃ and the time is 2-3 hours.
Further, in the step (2), the volume ratio of the NaOH solution to the N, N-Dimethylacetamide (DMA) is 1: 8-14, preferably 1: 9-12; the concentration of the NaOH solution is 0.05-0.2 mol/L.
Further, in the step (2), in the suspension, the mass percentage of the sodium lignosulfonate polycondensate in the mixed solution is 6-12%, preferably 7-9%.
Further, in the step (2), the mass ratio of the sodium lignosulfonate polycondensate to the glycidol trimethyl ammonium chloride is 1: 8-20, preferably 1: 8-14, and more preferably 1: 9-10.
Further, in the step (2), the reaction temperature is 55-75 ℃, and the reaction time is 7-10 hours.
Further, in the step (1) and the step (2), the washing is carried out until the washing liquid is neutral, the drying temperature is 40-70 ℃, and the drying is carried out until the weight is constant.
The application of the amphoteric adsorption material obtained by the preparation method in simultaneously removing anionic and cationic dyes in wastewater comprises the following steps: and adding an amphoteric adsorption material into the dye solution, then oscillating at constant temperature, measuring the residual concentration of the dye in the filtrate, and calculating the removal rate of the amphoteric adsorption material on the negative dye and the positive dye.
Further, the using amount of the amphoteric adsorption material is 0.1-0.5 g/L of dye solution, preferably 0.2-0.25 g/L of dye solution; the concentration of the dye solution is 20-80 mg/L; the dye solution is a dye solution containing methylene blue or/and Congo red.
Further, constant-temperature oscillation is carried out in a constant-temperature oscillator, the temperature is 29-31 ℃, and the oscillation adsorption reaction time is 10-24 hours.
Furthermore, the sum of the amounts of the methylene blue and the Congo red is fixed, and the molar ratio is 0-3.0: 3.0-0.
The invention has the beneficial effects that:
(1) the glycidol trimethyl ammonium chloride modified lignosulfonate polymer is used for preparing the amphoteric adsorbing material, the operation is simple, the cost is low, and no secondary pollution is caused.
(2) The amphoteric adsorbing material prepared by modifying the lignosulfonate polycondensate with the glycidol trimethyl ammonium chloride can adsorb anionic dye Congo red and cationic dye methylene blue simultaneously, and the adsorption capacities of the amphoteric adsorbing material are respectively 271 mg/g and 171mg/g when the adsorption percentages respectively reach 90% and 57%.
Drawings
FIG. 1 shows the adsorption rate of Congo red adsorbed by amphoteric adsorbing materials prepared at different reaction temperatures.
FIG. 2 shows the removal rate of Congo red adsorbed by amphoteric adsorbent materials prepared at different reaction times.
Figure 3 effect of dosing on congo red adsorption on amphoteric sorbent material.
FIG. 4 effect of dose on methylene blue adsorption on amphoteric sorbent materials.
Fig. 5 shows the adsorption capacity and separation factor of amphoteric adsorbent material for adsorbing congo red and methylene blue simultaneously.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 55 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 2
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 60 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 3
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 65 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 4
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 70 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 5
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 75 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 6
0.01g of each of the amphoteric adsorbents prepared in examples 1 to 5 was added to 50mL of Congo red solution having a concentration of 60mg/L, and after adsorption reaction for 10 to 24 hours in a shaker at 30 ℃ at a shaking speed of 130rpm, the concentration of the residual Congo red in the supernatant was measured, and the removal rate of Congo red adsorbed by the adsorbent was calculated.
Fig. 1 shows the removal rates of congo red adsorbed by amphoteric adsorbent materials prepared at different reaction temperatures, which are 78.6%, 83.45%, 90.23%, 89.55% and 87.53%, respectively. The ratio of glycidyl trimethyl ammonium chloride grafted to the lignosulfonate polycondensate was highest at a temperature of 65 ℃.
Example 7
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed, stirred for 3.5 hours at 80 ℃, then concentrated hydrochloric acid is dropwise added to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 7 hours at 65 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 8
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 8 hours at 65 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 9
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed and stirred for 3.5 hours at 80 ℃, concentrated hydrochloric acid is added dropwise to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 9 hours at 65 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 10
2mL of 1mol/L NaOH solution, 40mL of formaldehyde and 0.5g of sodium dodecyl benzene sulfonate are sequentially added into 100mg/L of 200mL of sodium lignosulfonate solution, uniformly mixed, stirred for 3.5 hours at 80 ℃, then concentrated hydrochloric acid is dropwise added to adjust the pH value of the mixed solution to 2, and then the mixed solution is continuously stirred for 3 hours at 95 ℃. Filtering to obtain filter residue which is the lignosulfonate polycondensate, washing the filter residue to be neutral by deionized water, and drying to constant weight. A0.1 mol/L NaOH solution and N, N-Dimethylacetamide (DMA) were mixed in a volume ratio of 1: 10. Suspending the obtained sodium lignosulfonate polymer in a mixed solution of NaOH solution and N, N Dimethylacetamide (DMA) with the content of 8 wt%, stirring for 10min, adding glycidol trimethyl ammonium chloride and the lignosulfonate polymer into the suspension in a mass ratio of 10:1, reacting for 10 hours at 65 ℃, cooling, filtering, washing filter residues to be neutral by deionized water, and drying in a 50 ℃ oven to constant weight.
Example 11
0.01g of each of the amphoteric adsorbents prepared in examples 7 to 10 was added to 50mL of Congo red solution having a concentration of 60mg/L, and after adsorption reaction for 10 to 24 hours in a shaker at 30 ℃ at a shaking speed of 130rpm, the concentration of the residual Congo red in the supernatant was measured, and the removal rate of Congo red adsorbed by the adsorbent was calculated.
Fig. 2 shows that the removal rates of the adsorption of congo red by the amphoteric adsorption materials prepared at different reaction times are 83.5%, 90.3%, 90.6% and 90.5%, respectively. After 8 hours of reaction, glycidyltrimethylammonium chloride was maximally grafted onto the lignosulfonate polycondensate, and a time of 8 hours is preferred from the viewpoint of economic cost.
Example 12
The amphoteric adsorbent prepared in example 8 was added to a Congo red solution having a concentration of 60mg/L at dosages of 0.1g/L, 0.111g/L, 0.125g/L, 0.143g/L, 0.167g/L, 0.2g/L, 0.25g/L, 0.333g/L and 0.5g/L, respectively. And (3) after adsorption reaction is carried out for 10-24 hours in a shaking table at the temperature of 30 ℃ and the shaking speed of 130rpm, measuring the concentration of the Congo red remained in the supernatant, and calculating the removal rate of the adsorption material to the Congo red.
FIG. 3 is a graph showing the effect of amphoteric adsorbent material additive amount on Congo Red adsorption. When the dosage is increased from 0.1g/L to 0.2g/L, the removal rate of the amphoteric adsorbing material to Congo red is increased from 48.1% to 90.23%, and when the dosage is more than 0.2g/L, the removal rate is not increased significantly, and the dosage is preferably 0.2g/L from the economic cost viewpoint.
Example 13
The amphoteric adsorbent prepared in example 8 was added to a methylene blue solution having a concentration of 20mg/L at dosages of 0.1g/L, 0.111g/L, 0.125g/L, 0.143g/L, 0.167g/L, 0.2g/L, 0.25g/L, 0.333g/L and 0.5g/L, respectively. And (3) after adsorbing and reacting for 10-24 hours in a shaking table at the temperature of 30 ℃ and the shaking speed of 130rpm, measuring the concentration of the residual methylene blue in the supernatant, and then calculating the removal rate of the adsorbing material to the methylene blue.
FIG. 4 shows the effect of adsorbent material addition dosage on adsorbing methylene blue, when dosage is increased from 0.1g/L to 0.2g/L, the removal rate of amphoteric adsorbent material on methylene blue is increased from 49.8% to 90.72%, when dosage is more than 0.2g/L, the increase of removal rate is not significant, and the dosage is preferably 0.2g/L in view of economic cost.
Example 14
Congo red and methylene blue are mixed in a molar ratio of 3:1, 2:1, 1:2 and 1:3 respectively, and the total substance amount of the two dyes is constant. Taking 0.01g of the amphoteric adsorbent prepared in example 8, adding the amphoteric adsorbent into a mixed solution of Congo red and methylene blue with a volume of 50mL respectively, carrying out adsorption reaction in a shaker at a shaking speed of 130rpm at a temperature of 30 ℃ for 10-24 hours, measuring the concentrations of the Congo red and the methylene blue remained in the supernatant respectively, calculating the adsorption capacities of the adsorbent for adsorbing the Congo red and the methylene blue respectively, and calculating the separation factors of the Congo red to the methylene blue and the methylene blue to the Congo red respectively.
The capacity of the amphoteric adsorbent material for adsorbing congo red and methylene blue simultaneously is shown in fig. 5. The amphoteric adsorbing material can adsorb anionic dye Congo red and cationic dye methylene blue at the same time, the separation factor of Congo red to methylene blue is always greater than 1, and the separation factor of methylene blue to Congo red is always less than 1, which indicates that the amphoteric adsorbing material tends to adsorb anionic dye Congo red in the mixed solution of anionic Congo red dye and cationic dye.

Claims (6)

1. The preparation method of the amphoteric adsorption material is characterized in that the amphoteric adsorption material is prepared by modifying lignosulfonate with glycidol trimethyl ammonium chloride, and specifically comprises the following steps:
(1) sequentially adding formaldehyde, NaOH solution and sodium dodecyl benzene sulfonate into sodium lignosulfonate solution, performing hydroxymethylation under an alkaline condition, adding hydrochloric acid, polymerizing into a water-insoluble sodium lignosulfonate polycondensate under an acidic condition, filtering, washing and drying, wherein the formaldehyde is used as a crosslinking agent, and the sodium dodecyl benzene sulfonate is used as an emulsifier;
the concentration of the sodium lignosulfonate solution is 50-200 mg/L; the concentration of the NaOH solution is 0.5-2 mol/L; the dosage ratio of the sodium lignosulfonate solution to the NaOH solution to the formaldehyde to the sodium dodecyl benzene sulfonate is 150-250 ml, 0.5-5 ml, 15-60 ml and 0.1-2 g;
carrying out hydroxymethylation reaction under the stirring condition, wherein the temperature is 60-80 ℃, and the time is 2-3.5 hours; adjusting the pH value of the mixed solution to 2-3 by hydrochloric acid, wherein the temperature of the polymerization reaction is 85-95 ℃, and the time is 2-3 hours;
(2) suspending the lignosulfonate polycondensate obtained in the step (1) in a mixed solution of N, N-Dimethylacetamide (DMA) and NaOH, wherein the volume ratio of the NaOH solution to the N, N-Dimethylacetamide (DMA) is 1: 8-14; the concentration of the NaOH solution is 0.05-0.2 mol/L, the mixture is uniformly stirred, glycidol trimethyl ammonium chloride is added into the uniformly stirred suspension for reaction, the mass ratio of the sodium lignosulfonate polycondensate to the glycidol trimethyl ammonium chloride is 1: 8-20, the reaction temperature is 55-75 ℃, the reaction time is 7-10 hours, and then the mixture is filtered, washed and dried to obtain the amphoteric adsorbing material capable of adsorbing anions and cations simultaneously.
2. The preparation method of the amphoteric adsorption material according to claim 1, wherein in the step (2), the mass percentage of the sodium lignosulfonate polycondensate in the mixed solution is 6-12% in the suspension.
3. The preparation method of the amphoteric adsorption material according to claim 1, wherein in the step (1) and the step (2), the washing is carried out until the washing liquid is neutral, the drying temperature is 40-70 ℃, and the drying is carried out until the weight is constant.
4. Use of the amphoteric adsorbent material obtained by the preparation method according to any one of claims 1 to 3 for simultaneously removing anionic and cationic dyes from wastewater, characterized by comprising the following steps: and adding an amphoteric adsorption material into the dye solution, then oscillating at constant temperature, measuring the residual concentration of the dye in the filtrate, and calculating the removal rate of the amphoteric adsorption material on the negative dye and the positive dye.
5. The application of the dye solution according to claim 4, wherein the amount of the amphoteric adsorptive material is 0.1-0.5 g/L of the dye solution; the concentration of the dye solution is 20-80 mg/L; the dye solution is a dye solution containing methylene blue or/and Congo red.
6. The application of claim 4, wherein the constant temperature shaking is carried out in a constant temperature shaker at 29-31 ℃ for 10-24 hours; the sum of the amounts of methylene blue and Congo red is fixed, and the molar ratio is 0-3.0: 3.0-0.
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