CN109052731B - Method for efficiently removing antimony from printing and dyeing wastewater - Google Patents
Method for efficiently removing antimony from printing and dyeing wastewater Download PDFInfo
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Abstract
The invention relates to the technical field of printing and dyeing wastewater treatment, and discloses a method for efficiently removing antimony from printing and dyeing wastewater aiming at the problem that the wastewater discharge exceeds the standard due to excessive antimony in the printing and dyeing wastewater, which comprises the following steps: filtering the printing and dyeing wastewater to obtain a pretreatment solution, adjusting the acidity of the pretreatment solution and adding a Fenton reagent for reaction, adjusting the pH of the pretreatment solution until floccules are generated, adding a flocculating agent and stirring for flocculation reaction, sending the pretreatment solution into an air flotation device to separate scum and water solution to obtain printing and dyeing reclaimed water with antimony removed, and preferably adding modified lignocellulose and a rice hull adsorption layer for filtration. According to the method, organic pollutants are firstly removed through Fenton reaction, then antimony and a small amount of heavy metal ions such as copper, chromium and zinc are removed through the generated ferric hydroxide and the flocculant, the antimony removal specificity is improved through the organic pollutant removal and heavy metal ion staged treatment, the antimony in the printing and dyeing wastewater is effectively removed, and the COD concentration and the concentration of other heavy metal ions are greatly reduced.
Description
Technical Field
The invention relates to the technical field of printing and dyeing wastewater treatment, in particular to a method for efficiently removing antimony from printing and dyeing wastewater.
Background
About 95% of the catalyst used in the polyester raw material synthesis process is antimony acetate or ethylene glycol antimony and other compounds, and the proportion of antimony element in the catalyst is about 40% according to the atomic weight of each element. Most of polyester fabrics or polyester blended fabrics need to be subjected to alkali desizing before printing and dyeing, and some of the polyester fabrics or polyester blended fabrics need to be subjected to special alkali deweighting treatment. The antimony is carried into the printing and dyeing wastewater in the treatment process. The national requirements for water pollution control are increasingly strict, water pollution control 'discharge standard of water pollutants for textile dyeing and finishing industry' is promulgated (GB 4287-2012), relevant enterprises are required to strictly execute the discharge requirements in the standards, wherein the standard modification in 2015 only puts forward the control requirement that the total antimony discharge is not higher than 0.1 mg/l. Under the condition that the use of the antimony-containing catalyst is not solved from the source of the chemical fiber product, many enterprises in the textile dyeing and finishing industry face the risk that the antimony in discharged water exceeds the standard.
Chinese patent CN201610423772.5, the name of which is a method for removing antimony from printing and dyeing wastewater, discloses a system for removing antimony from printing and dyeing wastewater consisting of a regulating tank, an air flotation tank, a hydrolysis tank, a biochemical tank, a secondary sedimentation tank and a tertiary sedimentation tank at 2016 (6/16), wherein the treatment system involves multiple processes such as acid regulation, air flotation treatment, hydrolysis, biochemical treatment and sedimentation, the system combination and process are complex, and a large amount of organic pollutants such as dye, slurry and auxiliary agent and a small amount of heavy metal ions such as copper, chromium, zinc and arsenic are also present in the printing and dyeing wastewater, and the components are complex, so the actual antimony removal effect is not ideal.
Disclosure of Invention
Aiming at the problem that the excessive antimony exists in the printing and dyeing wastewater to cause the wastewater discharge to exceed the standard, the invention aims to provide a method for efficiently removing antimony from the printing and dyeing wastewater, which can effectively remove antimony in the printing and dyeing wastewater, remove most organic pollutants and meet the discharge standard of the printing and dyeing wastewater.
The invention provides the following technical scheme:
a method for efficiently removing antimony from printing and dyeing wastewater comprises the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to an acidic range, then adding a Fenton reagent, and stirring for reaction;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value and stirring until floccules are generated;
(4) adding a flocculating agent into the pretreatment solution, and stirring for flocculation reaction;
(5) and then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed.
The method for removing antimony from printing and dyeing wastewater comprises the steps of removing solid matters from the printing and dyeing wastewater, adjusting pH to acidity, adding a Fenton reagent, removing organic pollutants in the printing and dyeing wastewater through an oxidation reaction of a strong oxidation system generated by the Fenton reagent reaction, greatly reducing COD concentration in the printing and dyeing wastewater, releasing and converting part of organic antimony into inorganic antimony ions, removing the interference of the organic pollutants on the removal of the subsequent antimony while removing the organic pollutants, adjusting the pH of the organic wastewater to convert ferric iron generated by the Fenton reaction into ferric hydroxide precipitate and form floc, so that the antimony in the printing and dyeing wastewater, metal ions such as copper, chromium, zinc and the like with lower concentrations and residual organic pollutants are adsorbed in a flocculation manner, and adding a flocculating agent to enhance the flocculation effect of the ferric hydroxide, so that the removal specificity of the antimony and other heavy metal ions is improved, the antimony removal effect is better. And then the wastewater is sent into an air floatation device to separate filter residue and water liquid, so as to obtain the printing and dyeing recovered water which is high in efficiency, free of antimony and effectively reduced in COD concentration and other heavy metal ion concentrations.
Preferably, the pH value of the pretreatment solution adjusted in the step (2) is 3-5, the Fenton reagent is a ferrous sulfate solution with the mass concentration of 8-15 wt% and a hydrogen peroxide solution with the mass concentration of 25-40 wt%, the hydrogen peroxide solution is added firstly, and then the ferrous sulfate solution is added, wherein the mass ratio of the hydrogen peroxide solution to the pretreatment solution is 1.2-2 wt%, the mass ratio of the ferrous sulfate to hydrogen peroxide is 3-8: 1, and the reaction time is 30-60 min. The strong oxidizing hydroxyl free radical formed by the reaction of the ferrous sulfate and the hydrogen peroxide can form a strong oxidizing atmosphere in the printing and dyeing wastewater. The excessive ferrous iron produces ferric iron as much as possible, and has strong ferrous reducibility, and the excessive ferrous iron is removed by flocculation through forming hydroxide precipitate in the subsequent treatment process.
Preferably, the pH value adjusted in step (3) is in the range of 6.5 to 9. Adjusting the pH value to 6.5-9 to form iron hydroxide floc, and converting metal ions such as copper, zinc, chromium and the like into hydroxide precipitate which is adsorbed by the iron hydroxide floc. Surface OH of floc due to iron hydroxide when pH is higher-Too much is not beneficial to the removal of antimony ions.
Preferably, the method of the invention further comprises the step (3) of adding modified lignocellulose with the mass of 1-2 wt% of the pretreatment liquid into the pretreatment liquid after the floccules are generated. Lignocellulose is organic flocculent fibrous matter, forms a three-dimensional network structure in printing and dyeing wastewater, has strong adhesive force to the iron hydroxide floccule and is mixed with the iron hydroxide floccule, and the flocculation effect of the iron hydroxide floccule is strengthened by adsorbing heavy metal ions including antimony.
Preferably, the modified lignocellulose is obtained by the following steps: dispersing and dissolving histidine in an MES buffer solution, wherein the mass proportion of the histidine is 1.0-2.0 wt%, adding polyethylene glycol condensed glyceryl ether with the mass proportion of 0.3-0.7 wt% of an MES buffer solution, uniformly dissolving, heating the buffer solution to 50-60 ℃, adding cellulose powder with the mass proportion of 2-3 wt% of the MES buffer solution, uniformly dispersing, performing ultrasonic-assisted oscillation for 30-60 min, freeze-drying, washing and drying again. Histidine and lignocellulose both contain hydroxyl, and the epoxypropyl group in the polyethylene glycol condensed glycerol ether can react with the hydroxyl, so the histidine is grafted to the surface of the lignocellulose by using the polyethylene glycol condensed glycerol ether as a cross-linking agent, the lignocellulose is insoluble in water and keeps a flocculent fiber state, heavy metal ions can be adsorbed and flocculated to strengthen the flocculation capability of the ferric hydroxide, histidine has amino and imidazolyl and is positively charged after being hydrolyzed in an aqueous solution, and in the alkaline range of the printing and dyeing wastewater under the action of the ferric hydroxide, namely the preferable pH is 6.5-9, antimony is mainly Sb (OH)6-、SbO3-The state exists, so that an ionic bond can be formed between the antimony and histidine with positive charge and imidazole groups, antimony is adsorbed on the lignocellulose, the adsorption and flocculation capacity of the lignocellulose and ferric hydroxide floc on antimony is enhanced, and compared with other heavy metal ions, the antimony removal efficiency of the printing and dyeing wastewater is improved.
Preferably, the step (5) further comprises adjusting the pH value of the water solution after the air flotation separation to 2-4, and then introducing the water solution into an adsorption tank containing a rice husk carbon adsorption layer for adsorption and filtration, wherein the flow rate of the water solution is 2-5 BV/h. Adjusting the water solution after flocculation separation to an acid range, so that the residual suspended hydroxide precipitate and antimony in the solution are converted into an ionic state and are adsorbed by the rice husk carbon, and meanwhile, the residual organic pollutants can also be adsorbed by the rice husk carbon, thereby further purifying the printing and dyeing wastewater and improving the removal efficiency of the antimony.
As a preferred method of the present invention, the rice husk char used is produced by the following process: dissolving phenolic resin in acetone, adding rice hull powder and potassium oxide, performing ultrasonic dispersion uniformly, evaporating and drying, calcining the obtained solid in nitrogen at 800-900 ℃ for 4-6 hours, and cooling to room temperature. The phenolic resin and the potassium oxide are loaded on the rice hull powder to be calcined in an oxygen-isolated manner, and the phenolic resin and the rice hull form an interpenetrating carbon skeleton cross-linked network after calcination, so that more pores and adsorption points are generated in the rice hull carbon, and the adsorption capacity of the rice hull carbon on micromolecule organic pollutants and heavy metal ions in the printing and dyeing wastewater is improved. And the potassium oxide is filled in the carbon skeleton cross-linked network after being melted and dissolved in an acidic aqueous solution, so that an alkaline atmosphere is formed inside the rice hull carbon, and adsorbed heavy metal ions are deposited in the rice hull carbon to strengthen the adsorption and removal of the heavy metal ions.
The preferable method is that the mass ratio of the rice hull powder to the phenolic resin to the potassium oxide is 2-3: 1-1.8: 1.2-2.
Preferably, the flocculating agent used in the step (4) is polyacrylamide, polyvinyl amide or polyethylene oxide, and the addition amount of the flocculating agent is 3-5 wt% of the mass of the pretreatment liquid. The flocculant is a nonionic flocculant, so that the applicability is strong, and the flocculation effect on heavy metal ions is good and the synergistic enhancement effect with the iron hydroxide floc is high through practice.
The invention has the following beneficial effects:
according to the method, organic pollutants are firstly removed by utilizing a Fenton reaction, then antimony and a small amount of heavy metal ions such as copper, chromium, zinc and the like are removed by utilizing the generated ferric hydroxide and a flocculating agent, the antimony removal specificity is improved by removing the organic pollutants and carrying out the stage treatment on the heavy metal ions, the antimony in the printing and dyeing wastewater is effectively removed, and the COD concentration and the concentrations of other heavy metal ions are greatly reduced.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
Example 1
A method for efficiently removing antimony from printing and dyeing wastewater comprises the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to 3, then adding a Fenton reagent, wherein the Fenton reagent is a ferrous sulfate solution with the mass concentration of 8% and a hydrogen peroxide solution with the mass concentration of 25wt%, adding the hydrogen peroxide solution firstly, then adding the ferrous sulfate solution, the mass ratio of the ferrous sulfate to hydrogen peroxide is 6:1, the mass ratio of the hydrogen peroxide solution to the pretreatment liquid is 2wt%, and stirring for fully reacting for 30 min;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value to 6.5, and stirring until floccules are generated;
(4) adding flocculant polyoxyethylene into the pretreatment liquid, wherein the addition amount is 3wt% of the mass of the pretreatment liquid, and stirring and reacting for 30 min;
(5) and then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 162 mu g/L to 26 mu g/L, the total antimony removal rate reduced to 83.9 percent, the COD concentration reduced from 215mg/L to 57mg/L, the COD removal rate reduced to 73.5 percent and the chroma removal rate reduced to 86.2 percent.
Example 2
A method for efficiently removing antimony from printing and dyeing wastewater comprises the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to 4, then adding a Fenton reagent, wherein the Fenton reagent is a ferrous sulfate solution with the mass concentration of 10% and a hydrogen peroxide solution with the mass concentration of 30wt%, adding the hydrogen peroxide solution firstly, then adding the ferrous sulfate solution, the mass ratio of the ferrous sulfate to hydrogen peroxide is 3:1, the mass ratio of the hydrogen peroxide solution to the pretreatment liquid is 1.6wt%, and stirring for reacting for 40 min;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value to 7, and stirring until floccules are generated;
(4) adding flocculating agent polyacrylamide into the pretreatment liquid, wherein the addition amount is 4 wt% of the mass of the pretreatment liquid, and stirring for reacting for 40 min;
(5) and then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 172 mu g/L to 27 mu g/L, the total antimony removal rate of 84.3 percent, the COD concentration reduced from 203mg/L to 52mg/L, the COD removal rate of 74.4 percent and the chroma removal rate of 87.1 percent.
Example 3
A method for efficiently removing antimony from printing and dyeing wastewater comprises the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to 5, then adding a Fenton reagent, wherein the Fenton reagent is a ferrous sulfate solution with the mass concentration of 15wt% and a hydrogen peroxide solution with the mass concentration of 40wt%, adding the hydrogen peroxide solution, adding the ferrous sulfate solution, wherein the mass ratio of the ferrous sulfate to the hydrogen peroxide is 3:1, and the mass ratio of the hydrogen peroxide solution to the pretreatment liquid is 1.2 wt%, and stirring and reacting for 60 min;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value, stirring for 9 till floccules are generated, adding modified lignocellulose with the mass of 1 wt% of the pretreatment liquid, and stirring;
(4) adding flocculant polyvinyl amide into the pretreatment liquid, wherein the addition amount is 5wt% of the mass of the pretreatment liquid, and stirring and reacting for 60 min;
(5) and then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed.
The modified lignocellulose used in the step (3) is obtained through the following processes: dispersing and dissolving histidine in MES buffer solution, wherein the mass proportion of the histidine is 1.0wt%, adding polyethylene glycol condensed glycerol ether with the mass proportion of 0.3wt% of MES buffer solution, dissolving uniformly, heating the buffer solution to 50 ℃, adding cellulose powder with the mass proportion of 2wt% of MES buffer solution, dispersing uniformly, oscillating for 30min with the assistance of ultrasound, freeze-drying, washing and drying again.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 178 mu g/L to 19 mu g/L, the total antimony removal rate of 89.3 percent, the COD concentration reduced from 224mg/L to 50mg/L, the COD removal rate of 77.7 percent and the chroma removal rate of 89.2 percent.
Example 4
A method for efficiently removing antimony from printing and dyeing wastewater comprises the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to 4, then adding a Fenton reagent, wherein the Fenton reagent is a ferrous sulfate solution with the mass concentration of 10wt% and a hydrogen peroxide solution with the mass concentration of 30wt%, adding the hydrogen peroxide solution, adding the ferrous sulfate solution, wherein the mass ratio of the ferrous sulfate to hydrogen peroxide is 6:1, and the mass ratio of the hydrogen peroxide solution to the pretreatment liquid is 1.8 wt%, and stirring for reaction for 50 min;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value, stirring the mixture for 7 hours until floccules are generated, adding 1.5 wt% of modified lignocellulose of the mass of the pretreatment liquid, and stirring the mixture;
(4) adding a flocculating agent polyacrylamide into the pretreatment liquid, wherein the adding amount is 4 wt% of the mass of the pretreatment liquid, and stirring for reacting for 40 min;
(5) and then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed.
Wherein, the modified lignocellulose used in the step (3) is obtained by the following processes: dispersing and dissolving histidine in MES buffer solution, wherein the mass proportion of the histidine is 1.6wt%, adding polyethylene glycol condensed glycerol ether with the mass proportion of 0.5wt% of MES buffer solution, dissolving uniformly, heating the buffer solution to 55 ℃, adding cellulose powder with the mass proportion of 2.5wt% of MES buffer solution, dispersing uniformly, oscillating for 40min with the assistance of ultrasonic, freeze-drying, washing and drying again.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced to 15 mu g/L from 180 mu g/L, the total antimony removal rate of 91.6 percent, the COD concentration reduced to 42mg/L from 225mg/L, the COD removal rate of 81.3 percent and the chroma removal rate of 91.2 percent.
Example 5
The method for efficiently removing antimony from printing and dyeing wastewater is different from the method in example 4 in that:
the modified lignocellulose used in the step (3) is obtained through the following processes: dispersing and dissolving histidine in MES buffer solution, wherein the mass proportion of the histidine is 2.0wt%, adding polyethylene glycol condensed glycerol ether with the mass proportion of 0.7wt% of MES buffer solution, dissolving uniformly, heating the buffer solution to 60 ℃, adding cellulose powder with the mass proportion of 3wt% of MES buffer solution, dispersing uniformly, oscillating for 60min with the assistance of ultrasound, freeze-drying, washing and drying again.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 169 mu g/L to 21 mu g/L, the total antimony removal rate reduced to 87.6 percent, the COD concentration reduced from 210mg/L to 45mg/L, the COD removal rate up to 78.6 percent and the chroma removal rate 90.2 percent.
Example 6
A method for efficiently removing antimony from printing and dyeing wastewater is different from the method in example 4,
in the step (5), the pretreatment liquid is sent into an air flotation device to separate scum and water liquid, the pH value of the water liquid is adjusted to 4, and then the water liquid is sent into an adsorption tank containing a rice hull carbon adsorption layer to be adsorbed and filtered, and the flow rate of the water liquid is 2BV/h, so that the printing and dyeing reclaimed water with antimony removed is obtained.
The rice husk charcoal is prepared by the following processes: dissolving phenolic resin in acetone, adding rice hull powder and potassium oxide, performing ultrasonic dispersion uniformly, evaporating and drying, calcining the obtained solid in nitrogen at 800 ℃ for 6 hours, and cooling to room temperature, wherein the mass ratio of the rice hull powder to the phenolic resin to the potassium oxide is 2:1: 2.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 175 mu g/L to 14 mu g/L, the total antimony removal rate of 92.0 percent, the COD concentration reduced from 226mg/L to 41mg/L, the COD removal rate of 81.8 percent and the chroma removal rate of 90.8 percent.
Example 7
A method for efficiently removing antimony from printing and dyeing wastewater is different from the method in example 4,
in the step (5), the pretreatment liquid is sent into an air flotation device to separate scum and water liquid, the pH value of the water liquid is adjusted to 3, and then the water liquid is sent into an adsorption tank containing a rice hull carbon adsorption layer to be adsorbed and filtered, and the flow rate of the water liquid is 4BV/h, so that the printing and dyeing reclaimed water with antimony removed is obtained.
The rice husk charcoal is prepared by the following processes: dissolving phenolic resin in acetone, adding rice hull powder and potassium oxide, performing ultrasonic dispersion uniformly, evaporating and drying, calcining the obtained solid in nitrogen at 850 ℃ for 5 hours, and cooling to room temperature, wherein the mass ratio of the rice hull powder to the phenolic resin to the potassium oxide is 3:1.5: 1.6.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced to 12 mu g/L from 183 mu g/L, the total antimony removal rate reduced to 93.4 percent, the COD concentration reduced to 37mg/L from 207mg/L, the COD removal rate up to 82.1 percent and the chroma removal rate up to 91.8 percent.
Example 8
A method for efficiently removing antimony from printing and dyeing wastewater is different from the method in example 4,
in the step (5), the pretreatment liquid is sent into an air flotation device to separate scum and water liquid, the pH value of the water liquid is adjusted to 2, and then the water liquid is sent into an adsorption tank containing a rice hull carbon adsorption layer to be adsorbed and filtered, and the flow rate of the water liquid is 5BV/h, so that the printing and dyeing reclaimed water with antimony removed is obtained.
The used rice husk carbon is prepared by the following processes: dissolving phenolic resin in acetone, adding rice hull powder and potassium oxide, performing ultrasonic dispersion uniformly, evaporating and drying, calcining the obtained solid in nitrogen at 900 ℃ for 4 hours, and cooling to room temperature, wherein the mass ratio of the rice hull powder to the phenolic resin to the potassium oxide is 3:1: 2.
The pretreatment liquid for the printing and dyeing wastewater treated by the method has the total antimony concentration reduced from 179 mu g/L to 14 mu g/L, the total antimony removal rate of 92.1 percent, the COD concentration reduced from 225mg/L to 41mg/L, the COD removal rate of 81.8 percent and the chroma removal rate of 90.9 percent.
Claims (7)
1. A method for efficiently removing antimony from printing and dyeing wastewater is characterized by comprising the following steps:
(1) pretreating printing and dyeing wastewater, and filtering to remove insoluble solid matters to obtain pretreatment liquid;
(2) adding acid liquor into the pretreatment liquid to adjust the pH value to an acidic range, then adding a Fenton reagent, and stirring for reaction;
(3) adding alkali liquor into the fully reacted pretreatment liquid, adjusting the pH value and stirring until floccules are generated;
(4) adding a flocculating agent into the pretreatment solution, and stirring for flocculation reaction;
(5) then sending the pretreatment liquid into an air flotation device to separate scum and water liquid to obtain printing and dyeing reclaimed water with antimony removed;
the step (5) also comprises the steps of adjusting the pH value of the water solution after the air flotation separation to 2-4, and then introducing the water solution into an adsorption tank containing a rice husk carbon adsorption layer for adsorption and filtration, wherein the flow rate of the water solution is 2-5 BV/h;
the used rice husk carbon is prepared by the following processes: dissolving phenolic resin in acetone, adding rice hull powder and potassium oxide, performing ultrasonic dispersion uniformly, evaporating and drying, calcining the obtained solid in nitrogen at 800-900 ℃ for 4-6 hours, and cooling to room temperature.
2. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 1, characterized in that the pH value of the pretreatment liquid adjusted in step (2) is 3-5, the Fenton reagents used are a ferrous sulfate solution with a mass concentration of 8-15 wt% and a hydrogen peroxide solution with a mass concentration of 25-40 wt%, the hydrogen peroxide solution is added firstly, and then the ferrous sulfate solution is added, wherein the mass ratio of the hydrogen peroxide solution to the pretreatment liquid is 1.2-2 wt%, the mass ratio of the ferrous sulfate to the hydrogen peroxide solution is 3-8: 1, and the reaction time is 30-60 min.
3. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 2, characterized in that the pH value adjusted in step (3) is in the range of 6.5-9.
4. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 1, 2 or 3, wherein the step (3) further comprises adding 1-2 wt% of modified lignocellulose of the mass of the pretreatment liquid to the pretreatment liquid after the flocs are generated.
5. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 4, characterized in that the modified lignocellulose is obtained by the following processes: dispersing and dissolving histidine in an MES buffer solution, wherein the mass proportion of the histidine is 1.0-2.0 wt%, adding polyethylene glycol condensed glyceryl ether with the mass proportion of 0.3-0.7 wt% of an MES buffer solution, uniformly dissolving, heating the buffer solution to 50-60 ℃, adding cellulose powder with the mass proportion of 2-3 wt% of the MES buffer solution, uniformly dispersing, performing ultrasonic-assisted oscillation for 30-60 min, freeze-drying, washing and drying again.
6. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 1, characterized in that the mass ratio of the rice hull powder, the phenolic resin and the potassium oxide is 2-3: 1-1.8: 1.2-2.
7. The method for efficiently removing antimony from printing and dyeing wastewater according to claim 1, 2 or 3, characterized in that the flocculating agent used in the step (4) is polyacrylamide, polyvinyl amide or polyethylene oxide, and the addition amount is 3-5 wt% of the mass of the pretreatment liquid.
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