CN107188293A - Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries - Google Patents
Method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries Download PDFInfo
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Abstract
The invention belongs to the field of wastewater treatment, and particularly relates to a method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries. The manganese-zinc ferrite prepared by waste batteries is combined with persulfate to form an advanced oxidation technology system, organic wastewater with azo dyes orange yellow II and bisphenol A as target pollutants is treated, the degradation effect is very good, the recycling performance of the manganese-zinc ferrite is good, and the activation performance of the manganese-zinc ferrite on the persulfate is superior to that of the manganese-zinc ferrite prepared by pure reagents according to the same method. The manganese-zinc ferrite has the advantages of high activation efficiency, low metal ion dissolution, easy separation after reaction and the like; the method takes the waste alkaline zinc-manganese battery as a raw material, and prepares the manganese-zinc ferrite after acid leaching and gelling, has the advantages of low cost, simple method and the like, and achieves the effect of recycling waste.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries.
Background
The yield and the usage amount of the alkaline zinc-manganese battery are large, and the mercury-free battery is realized, but the waste battery is treated as common garbage, so that the potential harm to the environment is caused, and the waste of resources is also caused. Organic wastewater is a kind of wastewater which is difficult to degrade, taking printing and dyeing wastewater as an example, the discharge amount is large, the content of organic pollutants is high, the types are complex, and the organic wastewater can bring serious pollution to the environment when entering water. Traditional treatment techniques have been severely challenged by the high toxicity, complex composition, and high chemical oxygen consumption of organic pollutants. It is difficult to achieve satisfactory treatment effects by applying conventional treatment techniques such as physical, chemical and biological methods and combinations thereof.
Advanced oxidation technology, characterized by producing large amounts of a substance having strong oxidizing powerOH is an oxidant to degrade macromolecular organic pollutants into micromolecules. Based on sulfate radicals (SO) 4 -.) is a new technology developed in recent years for oxidizing and degrading toxic organic pollutants. The activation of persulfates generally produces highly reactive sulfate radicals (SO) 4 -· ) Then, macromolecule and organic matter difficult to degrade in water are oxidized and degraded into low-toxicity or non-toxic micromolecule matter, even directly degraded into CO through addition, substitution, electron transfer, bond breaking and the like between free radicals and organic compounds 2 And H 2 O, near complete mineralization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing manganese-zinc ferrite activated persulfate degraded organic pollutants by using waste batteries.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the nickel-plated iron sheet, the manganese-zinc black solid and the zinc paste obtained in the step (1), wherein the dissolving solution is a mixed solution of a sulfuric acid solution and a hydrogen peroxide solution;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3), adjusting the molar ratio of the elements of iron, manganese and zinc, and adding citric acid monohydrate; then stirring the mixed solution for 3 to 4 hours under the condition of water bath at the temperature of between 25 and 30 ℃, and then adding a sodium hydroxide solution into the mixed solution to adjust the pH value to 4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(5) Drying, calcining, grinding and washing the solid obtained in the step (4) to be neutral to obtain manganese-zinc ferrite;
(6) And (3) placing the organic wastewater into a heterogeneous activation reactor, adding the manganese-zinc ferrite and persulfate obtained in the step (6), and finishing the degradation reaction of the organic pollutants at room temperature.
In the above scheme, the dissolving conditions in step (2) are as follows: heating and refluxing in water bath at 60-80 deg.c for 1-2 hr.
In the above scheme, the volume ratio of the sulfuric acid solution to the hydrogen peroxide solution in the step (2) is 50.
In the scheme, the solid-liquid ratio of the dissolution in the step (2) is 1.
In the scheme, the molar ratio of the elements Fe, mn and Zn in the step (4) is Fe: mn: zn =2:0.4:0.6.
in the above scheme, the molar ratio of the element Fe to citric acid monohydrate is 1: 1.5-1: 2.0.
in the scheme, the concentration of the sodium hydroxide solution in the step (4) is 0.1-20 mol/L.
In the scheme, the calcining temperature in the step (5) is more than or equal to 400 ℃, and the calcining time is 2 hours.
In the scheme, the organic wastewater in the step (6) is azo dye orange II wastewater or bisphenol A wastewater.
In the scheme, the concentration of the persulfate in the step (6) is 0.5-40 mmol/L, and the concentration of the manganese-zinc ferrite is 0.2-0.5 g/L.
In the scheme, the time of the degradation reaction is 20 min-150 min.
The invention has the beneficial effects that: (1) The manganese-zinc ferrite prepared by waste batteries is combined with persulfate to form an advanced oxidation technology system, the degradation effect of treating organic wastewater taking azo dye orange II as a target pollutant is very good, and when the manganese-zinc ferrite is combined with 2mmol/L potassium hydrogen persulfate, the decolorization rate reaches 97.9 percent within 30 minutes; when the manganese-zinc ferrite is combined with 10mmol/L sodium persulfate, the decolorization rate reaches 97.1 percent within 30 minutes; (2) The degradation experiment of the system on the bisphenol A shows that the system can achieve good degradation effect on the bisphenol A, the manganese-zinc ferrite has good recycling performance, and the activation performance of the system on persulfate is superior to that of the manganese-zinc ferrite prepared by pure reagents according to the same method; (3) The manganese-zinc ferrite has the advantages of high activation efficiency, low metal ion dissolution, easy separation of a catalyst (manganese-zinc ferrite) after reaction and the like, and has mild reaction conditions and good treatment effect; (4) The method takes the waste alkaline zinc-manganese batteries as raw materials, and prepares the manganese-zinc ferrite after acid leaching and gelling, has the advantages of low cost, simple method and the like, and achieves the effect of recycling wastes.
Drawings
FIG. 1 is a comparison of the oxidative degradation of orange II by a heterogeneous activated oxone system, with initial concentrations of orange II: 50mg/L, dosage of potassium hydrogen persulfate: 2mM, manganese zinc ferrite dosage: 0.5g/L.
FIG. 2 is a comparison of the oxidative degradation of orange II by a heterogeneous activated sodium persulfate system, with initial concentrations of orange II: 50mg/L, sodium persulfate dosage: 10mM, manganese zinc ferrite dosage: 0.5g/L.
FIG. 3 is a comparison of the oxidative degradation of bisphenol A by a heterogeneously activated oxone system, the initial concentration of bisphenol A: 0.1mM, amount of potassium hydrogen persulfate: 0.5mM, manganese zinc ferrite dosage: 0.2g/L.
FIG. 4 shows the recycling effect of manganese zinc ferrite for oxidizing and degrading bisphenol A by a heterogeneous activated oxone system, the initial concentration of bisphenol A: 0.1mM, potassium hydrogen persulfate dosage: 0.5mM, manganese zinc ferrite dosage: 0.2g/L.
FIG. 5 is a comparison of manganese-zinc ferrite prepared from waste battery extract and manganese-zinc ferrite prepared from pure reagent in the same method for oxidizing and degrading bisphenol A by heterogeneous activating oxone system, the initial concentration of bisphenol A: 0.1mM, potassium hydrogen persulfate dosage: 0.5mM, manganese zinc ferrite dosage: 0.2g/L.
FIG. 6 is an X-ray diffraction pattern of manganese-zinc ferrite prepared by the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the solids in the step (1), wherein the dissolving solution is 3-5 mol/L sulfuric acid, and the solid-liquid ratio is 1: 10-1: 15, adding a small amount of 30% (volume fraction) hydrogen peroxide, wherein the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:50, heating and refluxing in water bath at 60-80 ℃ for 1-2 hours;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3) to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0 of the total weight of the mixture;
(5) Stirring the mixed solution obtained in the step (4) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, stirring for 3-4 hours, and adding 0.1-20 mol/L sodium hydroxide solution into the mixed solution to adjust the pH to be =4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(6) Drying the solid obtained in the step (5), and then calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(7) And (3) placing simulated wastewater (the initial concentration is 50mg/L and 200 mL) containing orange II into a heterogeneous activation reactor, adding 0.1g of manganese-zinc ferrite obtained in the step (6) and 2mM of persulfate, and performing degradation reaction for 60min at room temperature.
The X-ray diffraction pattern of the manganese-zinc-ferrite of this example is shown in FIG. 6, and FIG. 1 is a comparison of the oxidative degradation of orange II by heterogeneous activated oxone system, as can be seen from FIG. 1: the degradation efficiency of the manganese zinc ferrite activated oxone system on orange II is obviously higher than that of the single oxone system. After the single potassium hydrogen persulfate is subjected to oxidation reaction for 60min, the decoloring rate of the orange II is less than 5%, and the decoloring rate of the orange II after the manganese zinc ferrite activates the potassium hydrogen persulfate to be oxidized for 30min reaches 97.9%. The iron ion elution concentration after the reaction was measured to be 0.020mg/L.
Example 2
A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the solids in the step (1), wherein the dissolving solution is 3-5 mol/L sulfuric acid, and the solid-liquid ratio is 1: 10-1: 15, adding a small amount of 30% (volume fraction) hydrogen peroxide, wherein the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:50, heating and refluxing in water bath at 60-80 ℃ for 1-2 hours;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking a filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3) to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0;
(5) Stirring the mixed solution obtained in the step (4) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, stirring for 3-4 hours, and adding 0.1-20 mol/L sodium hydroxide solution into the mixed solution to adjust the pH to be =4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(6) Drying the solid obtained in the step (5), and then calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(7) And (3) placing simulated wastewater (the initial concentration is 50mg/L and 200 mL) containing orange II into a heterogeneous activation reactor, adding 0.1g of manganese-zinc ferrite obtained in the step (6) and 10mM of persulfate, and performing degradation reaction for 60min at room temperature.
The X-ray diffraction pattern of the manganese-zinc-ferrite of the present example is shown in FIG. 6, FIG. 2 is a comparison of the oxidative degradation of orange II by heterogeneous activated oxone system, and it can be seen from FIG. 2 that the efficiency of degradation of orange II by the manganese-zinc-ferrite activated sodium persulfate system is significantly higher than that of the oxidation by sodium persulfate alone. After the single sodium persulfate is oxidized for 60min, the decoloring rate of the orange II is less than 6 percent, and the decoloring rate of the orange II after the manganese zinc ferrite is activated by the sodium persulfate and oxidized for 60min reaches 98.2 percent. The iron ion elution concentration after the reaction was measured to be 0.397mg/L.
Example 3
A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the solids in the step (1), wherein the dissolving solution is 3-5 mol/L sulfuric acid, and the solid-liquid ratio is 1: 10-1: 15, adding a small amount of 30% (volume fraction) hydrogen peroxide, wherein the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:50, heating and refluxing in water bath at 60-80 ℃ for 1-2 hours;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3) to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0;
(5) Stirring the mixed solution obtained in the step (4) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, stirring for 3-4 hours, and adding 0.1-20 mol/L sodium hydroxide solution into the mixed solution to adjust the pH to be =4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(6) Drying the solid obtained in the step (5), and then calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(7) A model wastewater (initial concentration: 0.1mM, 200mL) containing bisphenol A was placed in a heterogeneous activation reactor, 0.04g of the manganese-zinc ferrite obtained in step (6) and 0.1mM of persulfate were added, and a degradation reaction was carried out at room temperature for 60min.
The X-ray diffraction pattern of the manganese-zinc ferrite of the embodiment is shown in FIG. 6, FIG. 3 is a comparison of the oxidative degradation of bisphenol A by the heterogeneous activated oxone system, as can be seen in FIG. 3: the manganese zinc ferrite activated potassium hydrogen persulfate system also has good degradation effect on bisphenol A, and the degradation efficiency is obviously higher than that of the single potassium hydrogen persulfate oxidation. After the potassium hydrogen persulfate alone is subjected to oxidation reaction for 60min, the removal rate of the bisphenol A is 16.2%, and after the potassium hydrogen persulfate is activated by the manganese zinc ferrite to be oxidized for 60min, the removal rate of the bisphenol A reaches 96.2%. The dissolution of the manganese, the zinc and the iron after the reaction is very low.
Example 4
A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the solids in the step (1), wherein the dissolving solution is 3-5 mol/L sulfuric acid, and the solid-liquid ratio is 1: 10-1: 15, adding a small amount of 30% (volume fraction) hydrogen peroxide, wherein the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:50, heating and refluxing in water bath at 60-80 ℃ for 1-2 hours;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3) to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0 of the total weight of the mixture;
(5) Stirring the mixed solution obtained in the step (4) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, stirring for 3-4 hours, and adding 0.1-20 mol/L sodium hydroxide solution into the mixed solution to adjust the pH to be =4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(6) Drying the solid obtained in the step (5), and then calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(7) A model wastewater (initial concentration: 0.1mM, 200mL) containing bisphenol A was placed in a heterogeneous activation reactor, 0.04g of the manganese-zinc ferrite obtained in step (6) and 0.1mM of persulfate were added, and a degradation reaction was carried out at room temperature for 60min.
The X-ray diffraction pattern of the manganese-zinc ferrite of the present example is shown in FIG. 6, FIG. 4 is the effect of recycling manganese-zinc ferrite from oxidative degradation of bisphenol A by the heterogeneous activated oxone system, as can be seen from FIG. 4: the manganese-zinc ferrite activated potassium hydrogen persulfate system degrades bisphenol A, and the result of four-time repeated use experiments shows that when the initial concentration of bisphenol A is 0.1mM, the dosage of potassium hydrogen persulfate is 0.5mM, and the dosage of manganese-zinc ferrite is 0.2g/L, and the reaction time is 60min, the removal rate of bisphenol A by the first use of manganese-zinc ferrite is 95.7%; the removal rate of bisphenol A by using the manganese-zinc ferrite for the second time is 95.0 percent; the removal rate of the manganese-zinc ferrite on the bisphenol A for the third time is 90.7 percent; the removal rate of bisphenol A when the manganese-zinc ferrite is used for the fourth time is 84.6%. The results show that after 4 times of cyclic utilization, the BPA degrading performance of the catalyst is not obviously changed and still has good reaction activity. The metal dissolution conditions after four times of reactions are measured, and the results show that the dissolution of Mn, zn and Fe elements in the solution after repeated use is not improved, the Fe elements are not detected after four times of repeated tests, the dissolution concentration of the Mn element is between 0.6mg/L and 1.5mg/L, and the dissolution concentration of the Zn element is between 0.0mg/L and 0.123mg/L, further, the manganese-zinc ferrite has good stability in recycling and can be recycled.
Example 5
A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the solids in the step (1), wherein the dissolving solution is 3-5 mol/L sulfuric acid, and the solid-liquid ratio is 1:10 to 1:15, adding a small amount of 30% (volume fraction) hydrogen peroxide, wherein the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:50, heating and refluxing in water bath at 60-80 ℃ for 1-2 hours;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3) to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0;
(5) Stirring the mixed solution obtained in the step (4) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, stirring for 3-4 hours, and adding 0.1-20 mol/L sodium hydroxide solution into the mixed solution to adjust the pH to be =4; stopping stirring, setting the temperature of the water bath to be 60 ℃, and keeping for 1-2 hours; then setting the temperature of the water bath to 90 ℃, and keeping the temperature for 2 to 5 hours until no flowing liquid exists in the beaker;
(6) Drying the solid obtained in the step (5), and calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(7) And (3) placing simulated wastewater (the initial concentration is 50mg/L and 200 mL) containing bisphenol A into a heterogeneous activation reactor, adding 0.1g of manganese-zinc ferrite obtained in the step (6) and 2mM of persulfate, and carrying out degradation reaction for 60min at room temperature.
A method for degrading organic pollutants by using manganese-zinc ferrite activated persulfate prepared from waste batteries comprises the following steps:
(1) Weighing and mixing and dissolving manganese sulfate monohydrate, ferrous sulfate heptahydrate and zinc sulfate heptahydrate solid powder to ensure that the molar ratio of the elements Fe, mn and Zn is Fe: mn: zn =2:0.4:0.6, adding citric acid monohydrate to ensure that the molar ratio of the element Fe to the citric acid monohydrate is 1: 1.5-1: 2.0 of the total weight of the mixture;
(2) Stirring the mixed solution obtained in the step (1) under a water bath condition, controlling the water bath temperature to be 25-30 ℃, and stirring for 3-4 hours; then setting the temperature of the water bath to 60 ℃, and keeping for 1-2 hours; finally setting the water bath temperature to 90 ℃, and keeping the temperature for 2-5 hours until no flowing liquid exists in the beaker;
(3) Drying the solid obtained in the step (2), and then calcining the dried solid in the air atmosphere at the temperature of 400 ℃ for 2 hours; grinding and washing the calcined product to be neutral to obtain manganese-zinc ferrite;
(4) A model wastewater (initial concentration of 0.1mM, 200mL) containing bisphenol A was placed in a heterogeneous activation reactor, 0.04g of the manganese-zinc ferrite obtained in step (3) and 0.1mM of persulfate were added, and a degradation reaction was carried out at room temperature for 60min.
FIG. 5 is a comparison of the manganese-zinc ferrite prepared from the waste battery extract and the manganese-zinc ferrite prepared from the pure reagent in the heterogeneous activating oxone system for oxidative degradation of bisphenol A according to the same method. As can be seen from fig. 5: the reaction is carried out for 60min, the degradation efficiency of the pure reagent prepared manganese zinc ferrite activated potassium hydrogen persulfate on the bisphenol A is 69.3%, the degradation efficiency of the pure reagent prepared manganese zinc ferrite activated potassium hydrogen persulfate on the bisphenol A is 95.7%, and the degradation rate of the pure reagent prepared manganese zinc ferrite activated potassium hydrogen persulfate on the bisphenol A is slower than that of the pure reagent prepared manganese zinc ferrite activated potassium hydrogen persulfate on the waste battery extract. The possible reason is that the waste batteries also contain other metal elements, and the rest metal elements enter the manganese-zinc ferrite after acid leaching, and the oxidation-reduction property of various metals is different, so that the electron transfer is facilitated in the catalysis process, and the synergistic effect is generated, so that the reaction is accelerated.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. A method for preparing manganese-zinc ferrite activated persulfate from waste batteries to degrade organic pollutants comprises the following steps:
(1) Disassembling the alkaline zinc-manganese battery to obtain a nickel-plated iron sheet on the outer layer of the battery, a manganese-zinc black solid in the middle of the battery and zinc paste in the battery;
(2) Respectively dissolving the nickel-plated iron sheet, the manganese-zinc black solid and the zinc paste obtained in the step (1), wherein the dissolving solution is a mixed solution of a sulfuric acid solution and a hydrogen peroxide solution;
(3) Carrying out suction filtration on the three solutions obtained in the step (2) while the solutions are hot, taking a filtrate, and measuring the manganese ion content, the zinc ion content and the iron ion content in the three solutions;
(4) Mixing the three filtrates obtained in the step (3), adjusting the molar ratio of the elements of iron, manganese and zinc, and adding citric acid monohydrate; then stirring the mixed solution in a water bath at 25 to 30 ℃ for 3~4 hours, and adding a sodium hydroxide solution into the mixed solution to adjust the pH value to 4; stopping stirring, setting the water bath temperature to 60 ℃, and keeping the temperature for 1~2 hours; then setting the temperature of the water bath to 90 ℃, and keeping 2~5 hours until no flowing liquid exists in the beaker;
(5) Drying, calcining, grinding and washing the solid obtained in the step (4) to be neutral to obtain manganese-zinc ferrite;
(6) And (3) placing the organic wastewater into a heterogeneous activation reactor, adding the manganese-zinc ferrite and persulfate obtained in the step (5), and finishing the degradation reaction of the organic pollutants at room temperature.
2. The method for preparing manganese-zinc-ferrite activated persulfate to degrade organic pollutants by using waste batteries according to claim 1, wherein the dissolving conditions in the step (2) are as follows: heating and refluxing in a water bath at 60-80 ℃ for 8978 zxft For 8978 hours.
3. The method for preparing the manganese-zinc-ferrite activated persulfate degraded organic pollutants by using the waste batteries according to claim 1, wherein the volume ratio of the sulfuric acid solution to the hydrogen peroxide solution in the step (2) is 50 to 1, the molar concentration of the sulfuric acid solution is 3 to 5mol/L, and the volume fraction of the hydrogen peroxide solution is 30%.
4. The method for preparing the manganese-zinc-ferrite activated persulfate degraded organic pollutants by using the waste batteries according to claim 1, wherein the dissolved solid-to-liquid ratio in the step (2) is 1 to 10 to 1.
5. The method for preparing manganese-zinc ferrite activated persulfate to degrade organic pollutants by using waste batteries according to claim 1, wherein the molar ratio of the elements of iron, manganese and zinc in the step (4) is Fe: mn: zn =2:0.4:0.6.
6. the method for preparing manganese-zinc-ferrite activated persulfate to degrade organic pollutants by using waste batteries according to claim 1, wherein the molar ratio of the elemental iron to the citric acid monohydrate in the step (4) is 1:1.5 to 1:2.0.
7. the method for preparing the manganese-zinc-ferrite activated persulfate so as to degrade the organic pollutants by using the waste batteries as claimed in claim 1, wherein the concentration of the sodium hydroxide solution in the step (4) is 0.1 to 20mol/L.
8. The method for preparing the manganese-zinc-ferrite activated persulfate so as to degrade the organic pollutants by using the waste batteries according to claim 1, wherein the calcining temperature in the step (5) is more than or equal to 400 ℃, and the calcining time is 2 hours.
9. The method for preparing the manganese-zinc-ferrite activated persulfate degraded organic pollutants by using the waste batteries according to claim 1, wherein the concentration of the persulfate in the step (6) is 0.5-40 mmol/L, and the concentration of the manganese-zinc-ferrite is 0.2-0.5 g/L.
10. The method for preparing the manganese-zinc-ferrite activated persulfate degraded organic pollutants by using the waste batteries as claimed in claim 1, wherein the time of the degradation reaction in the step (6) is from 20min to 150min.
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