CN115925085A - Based on Fe 3+ Method for green and efficient degradation of endocrine disruptors in water by persulfate system - Google Patents
Based on Fe 3+ Method for green and efficient degradation of endocrine disruptors in water by persulfate system Download PDFInfo
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- persulfate
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000598 endocrine disruptor Substances 0.000 title claims abstract description 38
- 231100000049 endocrine disruptor Toxicity 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims description 28
- 230000015556 catabolic process Effects 0.000 title claims description 24
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims abstract description 187
- 235000004883 caffeic acid Nutrition 0.000 claims abstract description 95
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- 230000000593 degrading effect Effects 0.000 claims abstract description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 157
- 230000035484 reaction time Effects 0.000 claims description 7
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- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to the field of water treatment, and particularly relates to a Fe-based water treatment agent 3+ A method for degrading endocrine disruptors in water in a green and high-efficiency manner by adopting a persulfate system. The method comprises the steps of adding caffeic acid, ferric sulfate and persulfate into water to be treated containing endocrine disrupters, reacting in a reaction system under stirring, and degrading and removing the endocrine disrupters. Caffeic acid added in the invention, as a common natural organic phenolic acid, widely exists in natural plants, is environment-friendly, can efficiently promote the reduction of Fe (III) and effectively promote the activation of persulfate. Meanwhile, the caffeic acid has chelation property on iron ions, so that the dissolution rate of the iron ions can be increased, and the utilization rate of the iron ions is improved. Therefore, the invention can be used as the method for adding caffeic acid at the same timeReducing agent and chelating agent for effectively increasing Fe 3+ The catalytic efficiency of the persulfate catalytic system is improved, the applicable pH environment of the catalytic system is further expanded, and the industrial application prospect is wide.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a method for increasing Fe content by adding caffeic acid 3+ Method for removing endocrine disruptors in water by persulfate, and aims to solve Fe problem 3+ The problem of low degradation efficiency in the persulfate activation process is solved, and a new method which is more efficient, simple, convenient and green is found.
Background
In recent years, the global plastic industry has been vigorously developed, and it has been a normal practice to produce and use plastic articles on a large scale. Bisphenol a (BPA) is industrially used for synthetic polycarbonate plastics and plastic products such as epoxy resins, and thus BPA is present in various daily plastic products including mineral water bottles, medical instruments, and interior coatings for foods and beverages. There are 2700 million tons worldwide each year of BPA-containing plastics, BPA becoming one of the highest production and consumption chemicals worldwide. However, numerous animal experiments and epidemiological studies have shown that bisphenol a is an Endocrine Disrupter (EDC) and is not only a threat to fetal and childhood health, but is also thought to be closely related to obesity caused by cancer and metabolic disorders. Although bisphenol a has low solubility in water, large-scale production and heavy use result in bisphenol a being present in a variety of environmental media, including surface water, groundwater, soil, sediment, and air. It is reported that the concentration of bisphenol A in wastewater from wastewater treatment plants is as high as 370. Mu.g/L, while the concentration in surface water is 56. Mu.g/L. Therefore, there is a need to find an effective method for removing bisphenol a from water.
In recent years, based on sulfate radicals (SO) 4 - The advanced oxidation technology has strong oxidation capacity, mild reaction conditions and wide applicable pH range, and is widely applied to removal of pollutants in wastewater and remediation of soil. Compared with other persulfate activation technologies, such as ultraviolet light irradiation, ultrasound or heat treatment, the transition metal activation is more efficient and the operation is simpler. Ferrous ion (Fe) as one of the common metal activators 2+ ) Activated Persulfate (PMS) is widely of concern to scholars for its cost effectiveness and environmental friendlinessAnd (6) note. However, the slow rate of conversion of Fe (III) to Fe (II) during the reaction is a major limiting factor leading to a low catalytic efficiency. Reducing agents can be added to accelerate the reduction of Fe (III) or chelating agents can be added to prolong the reaction time.
Conventional Fe 2+ The persulfate activation system has the problems of non-lasting reaction, narrow pH application range, easy generation of iron mud or low efficiency of treating refractory organic pollutants and the like. The existing common iron reducing agents, such as hydroxylamine, although highly reducing, are toxic and introduce new contaminants. Common chelating agents, such as EDTA, are highly chelating but are not conducive to biodegradation and can be environmentally unfriendly. Therefore, the search for a reduction/chelating agent which has strong reducibility, small influence by pH, environmental friendliness and high economical efficiency is the key to promote the application of the homogeneous metal activated persulfate system in practical engineering. Based on this, the invention provides a method for producing Fe 3+ The degradation system added with caffeic acid in the persulfate system degrades endocrine disrupters in water, improves the solubility of Fe (III) by chelating caffeic acid and Fe (III), accelerates Fe (III)/Fe (II) circulation by utilizing the reducibility of the caffeic acid, improves the activation rate of persulfate, and realizes the efficient removal of the endocrine disrupters in water.
Disclosure of Invention
The invention aims to provide a natural organic phenolic acid caffeic acid used for Fe and capable of being used as a reducing agent and a chelating agent simultaneously 3+ The method for removing the endocrine disruptors in water by activating persulfate, thereby overcoming the defects of the prior art that the persulfate is activated by metal ions in a homogeneous system, and being a novel degradation system and a novel degradation method for efficiently degrading the endocrine disruptors in water. According to the invention, caffeic acid is added, so that the strong reducibility of the caffeic acid is utilized to accelerate Fe (III)/Fe (II) circulation, and the chelation is utilized to enhance the dissolution rate of iron ions. The addition of the caffeic acid can further widen the pH range, has better catalytic performance under the condition of pH 3-9, overcomes the bottleneck that the metal ion activated persulfate advanced oxidation technology is only suitable for strong acid conditions, and has better economic, environmental, social and engineering application prospects.
The technical scheme adopted by the invention for solving the technical problems is as follows:
based on Fe 3+ The method comprises the steps of adding caffeic acid, ferric sulfate and persulfate into water to be treated containing endocrine disrupters, reacting the reaction system under stirring, degrading and removing the endocrine disrupters, wherein the reaction time is not less than 10min, and efficiently removing the endocrine disrupters in the water.
Preferably, the endocrine disruptor is bisphenol a. More preferably, the concentration of the bisphenol A in the water to be treated is 5-10mg/L. More preferably 5mg/L.
Preferably, the caffeic acid, ferric sulfate, and persulfate salts can be added to the water to be treated as a solid or as a corresponding aqueous solution.
Preferably, the caffeic acid and Fe in ferric sulfate 3+ The molar ratio of (1-3): 1, more preferably 2.
Preferably, the dosage of the ferric sulfate is Fe in the reaction system 3+ The initial concentration of (A) is 0.01 to 0.05 mmol/L.
Preferably, caffeic acid and ferric sulfate are added into the water to be treated and stirred, so that the caffeic acid and Fe can be obtained 3+ The full mixing is beneficial to better chelation, so that higher and more stable catalytic effect is achieved; the more preferable stirring time is not less than 1min, and the stirring time is determined according to the actual working condition, for example, the stirring time is 1min when the volume of the water to be treated is 100mL, so that the mixing of the caffeic acid and the ferric sulfate can be better realized; more preferably, the stirring is magnetic stirring at a stirring rate of 400rpm.
Preferably, the caffeic acid is prepared into a caffeic acid solution in advance, the solvent is water, and the caffeic acid solution is added into the water to be treated in the form of the caffeic acid solution, so that the caffeic acid can be better dispersed, and the subsequent degradation effect is further improved. More preferably, the preparation temperature of the caffeic acid solution is 30-55 ℃, so that the dissolution of caffeic acid can be further accelerated, and the solubility is provided; more preferably, the concentration of the caffeic acid solution is 10mmol/L; more preferably, the stirring during the preparation is magnetic stirring, and the stirring speed is 500rpm.
Preferably, the addition amount of the persulfate is 0.2-1.0 mmol/L of the initial concentration of the persulfate in the reaction system.
Preferably, the persulfate is at least one of a peroxymonosulfate and a peroxydisulfate, more preferably a peroxymonosulfate, and more preferably potassium hydrogen persulfate.
Preferably, the rate of stirring of the reaction is 400rpm.
Preferably, the temperature of the reaction is 20 to 28 ℃, more preferably 20 to 26 ℃. Higher or lower temperatures may also effect the reaction with corresponding effect, but considering energy saving, the temperature is defined herein as normal temperature.
Preferably, the pH of the reaction is 3 to 9, more preferably 5 to 7.
Preferably, the reaction time is 10 to 20min, more preferably 10 to 15min.
Preferably, the method specifically comprises the following steps:
(1) Preparing a caffeic acid solution;
furthermore, the preparation temperature is 30-55 ℃, and the dissolution speed and the solubility can be improved;
further, the caffeic acid solution is 10mmol/L;
further, the method is preferably magnetic stirring, and the stirring speed is 500rpm during preparation;
(2) Adding a caffeic acid solution and a ferric sulfate solution into the water to be treated containing the endocrine disrupters, and stirring; the caffeic acid and Fe 3+ Fully mixing and chelating to further improve and stabilize the subsequent degradation effect;
further, the concentration of bisphenol A in the water to be treated is 5-10mg/L, and more preferably 5mg/L;
further, the volume of the water to be treated is 100mL;
further, in the reaction system after adding the caffeic acid solution and the ferric sulfate solution, fe 3+ The concentration is 0.01 to 0.05mmol/L;
further, fe in the ferric sulfate solution 3+ The concentration is 5mmol/L;
further, caffeic acid and Fe 3+ In a molar ratio of (1-3): 1, more preferably 2;
further, the stirring speed is 500rpm, and the stirring time is 1min;
(3) Adding persulfate solution into the solution obtained in the step (2), and reacting for not less than 10min under the stirring condition to realize the efficient degradation and removal of the endocrine disrupter bisphenol A in water;
further, the persulfate is at least one of a peroxymonosulfate and a peroxydisulfate, and is more preferably a peroxymonosulfate;
further, in the reaction system after adding persulfate solution, the concentration of persulfate is 0.1-2.0 mmol/L;
further, the concentration of the persulfate in the persulfate solution is 50mmol/L;
further, the stirring speed is 400rpm; the uniform dispersion of the caffeic acid in the reaction system can be further ensured, and the full reaction is ensured;
further, the reaction temperature is 20-28 ℃, and more preferably 20-26 ℃;
further, the pH of the reaction is 3 to 9, more preferably 5 to 7;
further, the reaction time is 10 to 20min, more preferably 10 to 15min.
According to the technical scheme, the endocrine disruptors in the water to be treated are degraded and removed, the reaction time is about 10min, the removal rate is not lower than 90%, and the efficient degradation and removal effect of the endocrine disruptors is achieved.
The significance of the invention lies in solving the problem of Fe in a homogeneous system 3+ The problem of low catalytic efficiency in the persulfate activation process is solved, the problem that the catalytic capability of the existing homogeneous catalysis technology is greatly reduced in a neutral or weakly alkaline environment is solved, and the problems that the conversion rate of Fe (III) to Fe (II) is low, iron mud is easily generated, and the adding amount is increased are solved. Caffeic acid (CAFA) added by the invention is widely existed in natural plants as common natural organic phenolic acid, is environment-friendly, can efficiently promote the reduction of Fe (III) and effectively promote persulfateAnd (4) activating. Meanwhile, caffeic acid has chelation property on iron ions, so that the dissolution rate of the iron ions can be increased, the utilization rate of the iron ions can be improved, and Fe can be reduced 3+ Dosage, e.g. Fe in the experiments of the invention 3+ The activated persulfate degrades the bisphenol A by about 10 percent in 20 minutes, but after the caffeic acid is added, the degradation is carried out in Fe 3+ The concentration is reduced to 0.03mmol/L, and the degradation of bisphenol A can reach about 80 percent in 20 minutes. Therefore, the invention adds caffeic acid as a reducing agent and a chelating agent simultaneously, improves the dissolution rate of iron ions, and improves Fe 3+ The method has the advantages that the removal rate of the endocrine disrupter bisphenol A can reach more than 90% after reacting for about 10min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The caffeic acid has a catechol structure, can effectively reduce Fe (III) into Fe (II), effectively improve the activation efficiency of persulfate, and can also chelate with iron ions to prolong the activation time;
(2) The method can efficiently remove the endocrine disrupter bisphenol A in water, and the removal rate of the bisphenol A can reach more than 95 percent within about 10 min;
(3) persulfate/Fe 3+ The caffeic acid system still has strong BPA degradation capability under neutral or alkalescent conditions, and the removal rate of bisphenol A can still reach more than 95% within 15min under alkalescent conditions of pH = 9.0;
(4) The caffeic acid used in the invention is natural organic phenolic acid, has no pollution to the environment, further reduces the dosage of iron and reduces the resource investment;
(5) The method is simple to operate, easy to realize and wide in industrial application prospect.
Drawings
FIG. 1 is a schematic diagram showing the concentration of degraded bisphenol A with time under different conditions.
FIG. 2 is a graphical representation of the degradation of bisphenol A concentration over time at various initial pH conditions.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings. The present invention is not limited to the following specific examples, but includes any combination of the specific embodiments.
Example 1: based on Fe 3+ The method for degrading endocrine disruptors in water in a green and high-efficiency manner by adopting a persulfate system comprises the following steps:
1. preparing a caffeic acid solution at a certain temperature;
the dissolving temperature in the first step is 50 ℃;
the concentration of the caffeic acid solution in the first step is 10mmol/L;
in the first step, the stirring method is magnetic stirring, and the stirring speed is 500rpm.
2. Adding caffeic acid solution and ferric sulfate solution into a reaction bottle filled with bisphenol A water solution, and stirring for 1min to make caffeic acid and Fe 3+ Fully mixing; the pH of the mixed solution is 3.05;
the concentration of the bisphenol A aqueous solution in the step two is 5mg/L;
the volume of the bisphenol A aqueous solution in the step two is 100mL;
fe in the ferric sulfate solution in the second step 3+ The concentration is 5mmol/L, fe in the mixed solution 3+ The concentration is 0.05mmol/L;
the concentration of the caffeic acid in the caffeic acid solution in the step two is 10mmol/L, and the concentration of the caffeic acid in the mixed solution is 0.10mmol/L;
caffeic acid and Fe in step two 3+ The molar ratio in the mixed solution is 2;
in the second step, the stirring method is magnetic stirring, and the stirring speed is 400rpm.
3. And D, adding a persulfate solution into the mixed solution obtained in the step II, and starting the bisphenol A degradation reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction is carried out for 20min. Continuously stirring in the reaction to ensure that the caffeic acid is uniformly dispersed in the solution, and after the reaction is carried out for 10-15min, the bisphenol A in the water can be efficiently removed;
the persulfate in the third step is potassium hydrogen Persulfate (PMS);
the persulfate solution in the third step has the persulfate concentration of 50mmol/L and the mixed solution has the persulfate concentration of 0.50mmol/L;
the stirring mode in the third step is magnetic stirring, and the stirring speed is 400rpm.
PMS/Fe in FIG. 1 3+ the/CAFA is a schematic diagram of the change situation of the bisphenol A concentration in the reaction system with time in the reaction process of 20min in the embodiment, and it can be seen from the figure that the degradation reaction of the embodiment is efficient and rapid, the removal rate of the bisphenol A is up to 88.48% when the reaction is carried out for 10min, and the removal rate is up to 99% in 15min.
Example 2: this embodiment differs from example 1 in that Fe is used in step (2) 3+ The amount of (B) was 0.01 to 0.04mmol/L, and the other steps and parameters were the same as those in example 1. The results show that the effect is better as the addition amount of iron is larger, but after the addition amount of iron exceeds 0.05mmol/L, although the addition amount of iron is increased, the reaction rate and the effect are not obviously improved, and 0.01-0.05mmol/L is the best addition amount of the reaction in the invention in consideration of the economic principle.
TABLE 1 different Fe 3+ Effect of dosage on BPA degradation
Example 3: this embodiment differs from examples 1 and 2 in that caffeic acid and Fe are present in step two 3+ The molar ratio in the mixed solution is (1-3): 1, other steps and parameters were the same as in example 1-2.
TABLE 2 different caffeic acids and Fe 3+ Effect of molar ratio on degradation of BPA
Example 4: the difference between the embodiment and the embodiment 1-3 is that the concentration of the persulfate in the reaction system in the step three is 0.1-2.0 mmol/L, and other steps and parameters are the same as those in the embodiment 1-3.
TABLE 3 Effect of different persulfate loadings on BPA degradation
As can be seen from Table 3, when the persulfate is added in too small an amount, i.e., 0.10mmol/L, bisphenol A in the system is not degraded, probably because caffeic acid itself, which is an organic substance, can compete for free radicals. Thus, the radicals generated by the activated persulfate may first react with caffeic acid, resulting in no degradation of bisphenol A. The persulfate is added in an amount exceeding 0.50mmol/L, so that the degradation of the bisphenol A is inhibited, and the inhibition effect is more obvious when the persulfate is added in a larger amount.
Example 5: adjusting pH, and performing caffeic acid to strengthen Fe under different initial pH conditions 3+ The experiment for degrading the bisphenol A in the water by the persulfate is carried out according to the following steps:
1. preparing a caffeic acid solution at a certain temperature;
the dissolving temperature in the first step is 50 ℃;
the concentration of the caffeic acid solution in the first step is 10mmol/L;
in the first step, the stirring method is magnetic stirring, and the stirring speed is 500rpm.
2. Adding persulfate solution into a reaction bottle filled with bisphenol A aqueous solution, stirring for 1min, fully mixing, and then using NaOH solution and/or H 2 SO 4 Adjusting the pH of the mixed solution to 5, 7, 9 and 11 respectively;
the concentration of the bisphenol A aqueous solution in the step two is 5mg/L;
the volume of the bisphenol A aqueous solution in the step two is 100mL;
the persulfate in the second step is potassium hydrogen Persulfate (PMS);
the concentration of the persulfate in the persulfate solution in the step two is 50mmol/L, and the concentration of the persulfate in the mixed solution is 0.50mmol/L;
NaOH solution and H in step two 2 SO 4 The concentration of the solution is 0.1mol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. And (5) adding a caffeic acid solution into the mixed solution obtained in the step two, fully stirring and mixing, adding a ferric sulfate solution, and starting the bisphenol A degradation reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction is carried out for 20min. Continuously stirring in the reaction to ensure that the caffeic acid is uniformly dispersed in the solution, and after the reaction is carried out for 10-15min, the bisphenol A in the water can be efficiently removed;
fe in the ferric sulfate solution in the third step 3+ The concentration is 5mmol/L, fe in the mixed solution 3+ The concentration is 0.05mmol/L;
the caffeic acid concentration in the caffeic acid solution in the third step is 10mmol/L, and the caffeic acid concentration in the mixed solution is 0.10mmol/L;
caffeic acid and Fe as described in step three 3+ The molar ratio in the mixed solution is 2;
the stirring method in the third step is magnetic stirring, and the stirring speed is 400rpm.
In this example, the pH application range of the method of the present invention is tested by adjusting the initial pH condition of the reaction, and the conditions and results of the initial pH of 3.05 in example 1 are combined to obtain a schematic diagram of the change of the concentration of bisphenol a in the reaction system with the reaction time when the method of the present invention is used for degrading bisphenol a in water under different pH conditions as shown in fig. 2, as can be known from the diagram, the system has good degradation capability under the condition of pH = 3.05-7.0, the removal rate can exceed 95% at pH 5 and 7 in 10min, and the removal rate of bisphenol a can still reach more than 95% within 15min even under the weakly alkaline condition of pH =9.0, so the catalytic system of the present invention has a wide pH application condition.
The following experimental examples under different working conditions are combined with example 1 to further embody the catalytic effect of the catalytic system of the invention:
the first experimental example: the oxidation experiment of bisphenol A by adding Persulfate (PMS) alone is carried out according to the following steps:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding a persulfate solution, adding the persulfate solution into the reaction bottle in the step one, continuously stirring, controlling the reaction temperature to be 25 +/-1 ℃ and reacting for 20min, and completing the oxidation experiment of the singly added persulfate on the bisphenol A;
the persulfate in the second step is potassium hydrogen Persulfate (PMS);
the concentration of the persulfate in the persulfate solution in the second step is 50mmol/L, and the concentration of the persulfate in the mixed solution is 0.50mmol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
Experiment example two: fe 3+ The oxidation experiment of activated persulfate on bisphenol A was carried out as follows:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding a persulfate solution, adding the persulfate solution into the reaction bottle in the step one, controlling the reaction temperature to be 25 +/-1 ℃, and fully stirring and mixing for 1min;
the persulfate in the second step is potassium hydrogen Persulfate (PMS);
the concentration of the persulfate in the persulfate solution in the second step is 50mmol/L, and the concentration of the persulfate in the mixed solution is 0.50mmol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. Adding ferric sulfate solution into the mixed solution, and continuously stirring in the reaction to ensure that ferric sulfate is mixed with sodium sulfateThe sulfate fully reacts for 20min to complete Fe 3+ Experiments with oxidative removal of bisphenol a by activated persulfate;
fe in the ferric sulfate solution in the third step 3+ The concentration is 5mmol/L, fe in the mixed solution 3+ The concentration is 0.05mmol/L;
the stirring method described in the third step is magnetic stirring, and the stirring speed is 400rpm.
Experiment example three: the experiment of removing bisphenol A by using caffeic acid to activate persulfate is carried out according to the following steps:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding a persulfate solution, adding a percaffeic acid solution into the reaction bottle in the step one, controlling the reaction temperature to be 25 +/-1 ℃, and fully stirring and mixing for 1min;
the persulfate in the second step is potassium hydrogen Persulfate (PMS);
the concentration of the persulfate in the persulfate solution in the step two is 50mmol/L, and the concentration of the persulfate in the mixed solution is 0.50mmol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. Adding caffeic acid solution into the mixed solution, continuously stirring in the reaction to ensure that the caffeic acid and the persulfate fully react, and completing the experiment of oxidizing and removing the bisphenol A by the caffeic acid activated sulfate after reacting for 20 min;
the caffeic acid concentration in the caffeic acid solution in the third step is 10mmol/L, and the caffeic acid concentration in the mixed solution is 0.10mmol/L;
the stirring method described in the third step is magnetic stirring, and the stirring speed is 400rpm.
Experimental example four: the experiment of removing bisphenol A by the synergy of caffeic acid and ferric sulfate is carried out according to the following steps:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding a caffeic acid solution, adding a persulfate solution into the reaction bottle in the step one, controlling the reaction temperature to be 25 +/-1 ℃, and fully stirring and mixing for 1min;
in the second step, the concentration of the caffeic acid in the caffeic acid solution is 10mmol/L, and the concentration of the caffeic acid in the mixed solution is 0.10mmol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. Adding ferric sulfate solution into the mixed solution, continuously stirring in the reaction to ensure that the caffeic acid and ferric sulfate fully react, and after reacting for 20min, completing the experiment of oxidizing and removing the bisphenol A by the caffeic acid and ferric sulfate;
fe in the ferric sulfate solution in the third step 3+ The concentration is 5mmol/L, fe in the mixed solution 3+ The concentration is 0.05mmol/L;
the stirring method described in the third step is magnetic stirring, and the stirring speed is 400rpm.
Experimental example five: fe 2+ The oxidation experiment of activated persulfate on bisphenol A was carried out as follows:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding a persulfate solution, adding the persulfate solution into the reaction bottle in the step one, controlling the reaction temperature to be 25 +/-1 ℃, and fully stirring and mixing for 1min;
the persulfate in the second step is potassium hydrogen Persulfate (PMS);
the concentration of the persulfate in the persulfate solution in the second step is 50mmol/L, and the concentration of the persulfate in the mixed solution is 0.50mmol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. Adding ferrous sulfate solution into the mixed solution, continuously stirring in the reaction to ensure that the ferrous sulfate fully reacts with the persulfate, and finishing the Fe reaction after 20min 3+ Experiments on the oxidative removal of bisphenol a by activated persulfate;
fe in the ferrous sulfate solution in the third step 2+ The concentration is 5mmol/L, fe in the mixed solution 2+ The concentration is 0.05mmol/L;
the stirring method described in the third step is magnetic stirring, and the stirring speed is 400rpm.
Experimental example six: caffeic acid in cooperation with Fe 2+ The oxidation experiments of bisphenol A with activated persulfate were carried out as follows:
1. preparing a bisphenol A aqueous solution: preparing a bisphenol A aqueous solution with a certain concentration and transferring the bisphenol A aqueous solution into a reaction bottle;
the concentration of the bisphenol A aqueous solution in the first step is 5mg/L;
the volume of the bisphenol A aqueous solution in the first step is 100mL.
2. Adding caffeic acid solution and ferrous sulfate solution into a reaction bottle filled with bisphenol A water solution, and stirring for 1min to make caffeic acid and Fe 2+ Mixing thoroughly, mixing with NaOH solution and H 2 SO 4 Adjusting the pH of the mixed solution to 3.05;
fe in the ferric sulfate solution in the second step 2+ The concentration is 5mmol/L, fe in the mixed solution 2+ The concentration is 0.05mmol/L;
the concentration of the caffeic acid in the caffeic acid solution in the step two is 10mmol/L, and the concentration of the caffeic acid in the mixed solution is 0.10mmol/L;
caffeic acid and Fe in step two 2+ The molar ratio in the mixed solution is 2;
NaOH solution and H as described in step two 2 SO 4 The concentration of the solution is 0.1mol/L;
the stirring method in the second step is magnetic stirring, and the stirring speed is 400rpm.
3. And D, adding a persulfate solution into the mixed solution obtained in the step II, and starting the bisphenol A degradation reaction. The reaction temperature is controlled at 25 +/-1 ℃ and the reaction is carried out for 20min. Continuously stirring in the reaction to ensure that the caffeic acid is uniformly dispersed in the solution;
the persulfate in the third step is potassium hydrogen Persulfate (PMS);
the persulfate solution in the third step has the persulfate concentration of 50mmol/L and the mixed solution has the persulfate concentration of 0.50mmol/L;
the stirring mode in the third step is magnetic stirring, and the stirring speed is 400rpm.
FIG. 1 is a schematic view showing the change of the concentration of degraded bisphenol A with time under different working conditions of example 1 and Experimental examples I to VI of the present invention, and Fe can be seen from the graph 3+ And Fe 2+ The effect of activating persulfate alone is not ideal, the degradation of bisphenol A is 9.47 percent and 16.03 percent respectively in 20 minutes, and Fe 2+ Relative to Fe 3+ A stronger activation effect is shown; after addition of caffeic acid, fe 3+ And Fe 2+ The degradation rate of the activated persulfate bisphenol A is obviously increased, and 88.48 percent and 69.57 percent can be respectively removed in only 10min, especially for Fe 3+ Has more obvious and efficient enhancing effect, so that the caffeic acid can effectively enhance Fe 3+ A persulfate system. Meanwhile, caffeic acid can not activate persulfate alone or persulfate can not directly degrade bisphenol A. It can be seen that only caffeic acid, fe, is described in the present invention 3+ And the persulfate is simultaneously existed in the catalytic system, so that the effect of efficiently degrading endocrine disruptors in water can be realized.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. Based on Fe 3+ The method for degrading endocrine disruptors in water in a green and high-efficiency manner by adopting the persulfate system is characterized by comprising the following stepsAdding caffeic acid, ferric sulfate and persulfate into the water to be treated containing the endocrine disrupters, and reacting under stirring for not less than 10min.
2. An Fe-based alloy according to claim 1 3+ The method for degrading the endocrine disruptors in water in a green and high-efficiency manner by adopting a persulfate system is characterized in that the endocrine disruptors are bisphenol A.
3. An Fe-based alloy according to claim 2 3+ The method for degrading endocrine disruptors in water in a green and high-efficiency manner by adopting a persulfate system is characterized in that the concentration of bisphenol A in water to be treated is 5-10mg/L.
4. An Fe-based alloy according to claim 1 3+ The green and efficient method for degrading endocrine disruptors in water by adopting the persulfate system is characterized in that caffeic acid and Fe 3+ The molar ratio of (1-3): 1.
5. an Fe-based alloy according to claim 1 3+ The method for green and efficient degradation of endocrine disruptors in water by adopting a persulfate system is characterized in that the adding amount of ferric sulfate is Fe in a reaction system 3+ The initial concentration of (A) is 0.01 to 0.05 mmol/L.
6. An Fe-based alloy according to claim 1 3+ A method for degrading endocrine disruptors in water in a green and efficient manner by using a persulfate system is characterized in that caffeic acid and ferric sulfate are added into water to be treated, stirring is carried out for not less than 1min, and persulfate is added.
7. An Fe-based alloy according to claim 1 3+ A method for degrading endocrine disruptors in water in a green and high-efficiency manner by using a persulfate system is characterized in that persulfate is at least one of peroxymonosulfate and peroxydisulfate, and the addition amount of persulfate is based on the initial addition amount of persulfate in the reaction systemThe concentration is 0.2-1.0 mmol/L.
8. An Fe-based alloy according to claim 1 3+ The method for degrading endocrine disruptors in water in a green and efficient manner by adopting a persulfate system is characterized in that the pH value of the reaction is 3-9.
9. An Fe-based alloy according to claim 1 3+ The method for green and efficient degradation of endocrine disruptors in water by a persulfate system is characterized in that the reaction temperature is 20-28 ℃ and the reaction time is 10-20min.
10. An Fe-based alloy according to claim 1 3+ The method for degrading endocrine disruptors in water in a green and efficient manner by using a persulfate system is characterized by comprising the following steps:
(1) Preparing a caffeic acid solution;
(2) Adding a caffeic acid solution and a ferric sulfate solution into the water to be treated containing the endocrine disruptors, and stirring;
(3) And (3) adding persulfate solution into the solution obtained in the step (2), and reacting for not less than 10min under the stirring condition to realize degradation and removal of endocrine disrupters bisphenol A in water.
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