1. A method for removing antibiotics in a water body by using chalcopyrite activated percarbonate is characterized in that the method is used for treating the antibiotics in the water body by using chalcopyrite as a catalyst to activate percarbonate; the chalcopyrite is CuFeS₂。

2. The method of claim 1, comprising the steps of: mixing the chalcopyrite, the percarbonate and the antibiotic water body for degradation reaction to finish the removal of the antibiotic in the water body.

3. The method according to claim 2, wherein the addition amount of the chalcopyrite is 0.1-0.8 g per liter of antibiotic water; the addition amount of the percarbonate is 0.5 mmol-1.0 mmol of percarbonate added in each liter of antibiotic water body.

4. The method according to claim 3, characterized in that the chalcopyrite preparation methodThe method comprises the following steps: mixing Cu⁺、Fe³⁺And S^2-Mixing, carrying out hydrothermal reaction, washing, filtering and drying to obtain the chalcopyrite.

5. The method of claim 4, wherein the Cu is⁺、Fe³⁺And S^2-The molar ratio of (A) to (B) is 1: 2; the Cu⁺Is CuCl or Cu₂SO₄At least one of; said Fe³⁺Is FeCl₃·6H₂O、Fe(NO₃)_3.9H₂O and Fe₂(SO₄)_3.9H₂At least one of O; said S^2-Is (NH)₄)₂S、Na₂S·9H₂At least one of O, thioacetamide and thiourea; the temperature of the hydrothermal reaction is 160-200 ℃; the time of the hydrothermal reaction is 8-12 h; the washing reagents adopted in the washing process are ethanol and ultrapure water; the drying temperature is 60-80 ℃; the drying time is 10-24 h.

6. A process according to claim 3, wherein the percarbonate is sodium percarbonate and/or potassium percarbonate.

7. The method according to any one of claims 1 to 6, wherein the antibiotic in the antibiotic water body comprises at least one of sulfadimidine, sulfamethoxazole, tetracycline and ciprofloxacin; the initial concentration of the antibiotics in the antibiotic water body is 1 mg/L-5 mg/L.

8. The method according to any one of claims 1 to 6, wherein the initial pH value of the antibiotic water body is 3.1 to 9.0.

9. The method according to any one of claims 2 to 6, wherein the degradation reaction is carried out under stirring conditions; the stirring speed is 200-400 rpm; the temperature of the degradation reaction is 15-45 ℃; the time for the degradation reaction was 45 min.

Background

Antibiotics have long been detected frequently in different environmental media, such as soil, wastewater from sewage treatment plants, rivers, ground water and drinking water, due to abuse problems of antibiotics. Sulfamethazine (SMT) is a typical bacteriostatic sulfonamide antibiotic that has been widely used in human medicine, poultry, and aquaculture industries. Although the concentration level of SMT in surface water is typically only ng/L to μ g/L, even trace concentrations pose a significant threat to ecosystem and human health. However, the conventional sewage treatment process has a poor effect on its removal due to the high frequency of its drug-resistant bacteria and drug-resistant genes. Therefore, it is necessary to develop an efficient and environmentally friendly water treatment technology to treat antibiotics (such as SMT) in water, which is beneficial to improving water quality safety and ecological civilization construction.

Sodium percarbonate (SPC, Na)₂CO₃·1.5H₂O₂) Is a solid hydrogen peroxide and liquid H₂O₂Compared with the prior art, the composite material has better stability, longer storage time and explosion-proof performance, and belongs to a nontoxic environment-friendly oxidant. In addition, the alkaline property of sodium percarbonate enables the percarbonate-based advanced oxidation technology to have a wider pH application range, and can effectively avoid acidification of a water environment, so that more and more attention is paid. Currently, the reported strategies for activating SPC to generate active species mainly include uv irradiation, transition metals, plasma discharge, biochar, and the like. Among them, transition metal activation is attracting much attention for environmental remediation. However, the prior art reported advanced oxidation technology of transition metal activated percarbonate uses a large amount of percarbonate, requires a long treatment time, is susceptible to inorganic and organic components in water, and has poor selectivity in removing pollutants from water, which makes the removal of pollutants from water difficultThe existing percarbonate-based advanced oxidation technology is still difficult to effectively remove antibiotics in water, so that the wide application of the percarbonate-based advanced oxidation technology in treating antibiotic wastewater is limited. To date, no reference to chalcopyrite (CuFeS) has been found₂) Activated percarbonate has been reported for use in the treatment of antibiotic wastewater. Therefore, how to obtain the method for removing the antibiotics in the water body, which has the advantages of simple process, short reaction time, good removal effect, wide pH application range and environmental friendliness, has very important significance for effectively treating the antibiotics in the water body.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides the method for removing the antibiotics in the water body by using the chalcopyrite activated percarbonate, which has the advantages of simple process, short reaction time, good removal effect, wide pH application range and environmental friendliness.

In order to solve the technical problems, the invention adopts the technical scheme that:

a method for removing antibiotics in a water body by using chalcopyrite activated percarbonate is disclosed, wherein the method uses chalcopyrite as a catalyst to activate percarbonate for treating the antibiotics in the water body; the chalcopyrite is CuFeS₂。

The method is further improved and comprises the following steps: mixing the chalcopyrite, the percarbonate and the antibiotic water body for degradation reaction to finish the removal of the antibiotic in the water body.

In the method, the addition amount of the chalcopyrite is further improved, and 0.1g to 0.8g of the chalcopyrite is added in each liter of antibiotic water body; the addition amount of the percarbonate is 0.5 mmol-1.0 mmol of percarbonate added in each liter of antibiotic water body.

In the above method, further improvement, the method for preparing chalcopyrite comprises the following steps: mixing Cu⁺、Fe³⁺And S^2-Mixing, carrying out hydrothermal reaction, washing, filtering and drying to obtain the chalcopyrite.

In a further improvement of the above method, the Cu⁺、Fe³⁺And S^2-In a molar ratio of 1: 12: 2; the Cu⁺Is CuCl or Cu₂SO₄At least one of; said Fe³⁺Is FeCl₃·6H₂O、Fe(NO₃)₃·9H₂O and Fe₂(SO₄)₃·9H₂At least one of O; said S^2-Is (NH)₄)₂S、Na₂S·9H₂At least one of O, thioacetamide and thiourea; the temperature of the hydrothermal reaction is 160-200 ℃; the time of the hydrothermal reaction is 8-12 h; the washing reagents adopted in the washing process are ethanol and ultrapure water; the drying temperature is 60-80 ℃; the drying time is 10-24 h.

In the above method, further improvement, the percarbonate is sodium percarbonate and/or potassium percarbonate.

In the above method, further improvement, the antibiotic in the antibiotic water body comprises at least one of sulfamethazine, sulfamethoxazole, tetracycline and ciprofloxacin; the initial concentration of the antibiotics in the antibiotic water body is 1 mg/L-5 mg/L.

In the method, the initial pH value of the antibiotic water body is further improved to be 3.1-9.0.

In the above method, further improvement, the degradation reaction is carried out under stirring conditions; the stirring speed is 200-400 rpm; the temperature of the degradation reaction is 15-45 ℃; the time for the degradation reaction was 45 min.

Compared with the prior art, the invention has the advantages that:

the invention provides a method for removing antibiotics in water by using chalcopyrite activated percarbonate, which is used for treating the antibiotics in the water by using chalcopyrite as a catalyst to activate the percarbonate, wherein the chalcopyrite is CuFeS₂. In the invention, the CuFeS₂Reduced sulfur species present on the surface, interaction between Cu (I) and Fe (III) on the surface, and superoxide radical (O) generated in the reaction system₂ ^·-) The combined action of (A) and (B) promotes CuFeS₂Redox cycling of surface Fe species, thereby allowing for neutral reaction mediumThe continuous and high-efficiency activation of percarbonate to generate multiple reactive substances with oxidizing power, including hydroxyl radical(s) ((^·OH), carbonate radical (CO)₃ ^·-)、O₂ ^·-And singlet oxygen (¹O₂) Finally, the antibiotics in the water body are oxidized by utilizing the reactive substances, so that the antibiotics in the water body are effectively removed, and taking Sulfadimidine (SMT) as an example, the method can effectively remove 86.4 percent of sulfadimidine in the water body within 45 min. In addition, the carbonate adopted in the invention has low price, safety and stability, easy storage and transportation, no microbial toxic effect on the final decomposition product, and the use of the percarbonate expands the CuFeS₂The application range of the process is within the range of pH value of 3.1-9.0, the process has good oxidation removal effect on antibiotics (such as sulfamethazine) in the water body, and the defect that the effect of the existing advanced oxidation technology for activating peroxide by metal sulfide on treating target pollutants in the water body under neutral and alkaline conditions is not ideal is overcome. In addition, the percarbonate also has a buffering effect, the use of the percarbonate can simultaneously avoid the problems of leaching of excessive toxic metal ions and acidification of treated effluent, and the total soluble iron ion and copper ion concentrations in the effluent are lower than 0.28mg/L, which is obviously superior to that based on CuFeS reported₂The advanced oxidation water treatment technology. Compared with other existing CuFeS₂Compared with the method for activating peroxide, the method has obviously better removal efficiency on antibiotics in a neutral reaction medium, and the removal efficiency is respectively 26.8 percent, 6.2 percent and 24.4 percent higher than the activation removal efficiency of common sodium persulfate, potassium peroxymonosulfate and hydrogen peroxide. The invention relates to a method for removing antibiotics in water by using chalcopyrite activated percarbonate, which adds chalcopyrite (CuFeS)₂) The method enhances the catalytic activation capability of percarbonate, obviously enhances the removal effect of the percarbonate on antibiotics, improves the removal rate by 6.2-26.8% compared with other transition metal materials, has the advantages of simple process, short reaction time, good removal effect, wide pH application range, environmental friendliness, no secondary pollution and the like, and has high use value and good application prospect.

Drawings

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.

Fig. 1 is a comparison graph of the removal effect of sulfamethazine in a water body under different treatment systems in example 1 of the present invention.

FIG. 2 shows the simultaneous reaction of CuFeS in example 2 of the present invention₂And the comparative graph of the removal effect of the sulfadimidine when the sodium percarbonate is added into water bodies with different pH values.

FIG. 3 is a graph showing the effect of sulfadimidine removal after sodium percarbonate is added to adjust the pH of the water in example 2 of the present invention.

Detailed Description

The examples further illustrate the invention without thereby limiting the scope of protection of the invention.

The materials and equipment used in the following examples are commercially available.

Example 1

A method for removing antibiotics in water body by using chalcopyrite activated percarbonate, specifically a method for removing antibiotics in water body by using CuFeS₂And sodium percarbonate to treat the sulfamethazine water body, comprising the following steps:

respectively adding CuFeS according to the addition amount of 0.5g/L and 0.8mmol/L₂And adding Sodium Percarbonate (SPC) into a sulfadimidine water body with an initial pH value of 3.1 and an initial concentration of 5mg/L, placing the obtained reaction system in a digital display constant-temperature water bath kettle for degradation reaction, and uniformly mixing by using an electric mechanical stirrer in the degradation reaction process, wherein the constant temperature treatment temperature of the water body is 25 ℃, the mechanical stirring rotation speed is 250rpm, and the treatment time is 45min, so that the sulfadimidine in the water body is removed.

Control group one (FeS)₂SPC): with FeS₂Replacing CuFeS₂The activated percarbonate is used for treating the sulfadimidine in the water body, and other conditions are the same.

Control group two (CuS/SPC): with CuSReplacing CuFeS₂The activated percarbonate is used for treating the sulfadimidine in the water body, and other conditions are the same.

Control group III (CuFeO)₂SPC): with CuFeO₂Replacing CuFeS₂The activated percarbonate is used for treating the sulfadimidine in the water body, and other conditions are the same.

Control group four (CuFeS)₂/PS): with CuFeS₂The activated Persulfate (PS) is used for treating the sulfadimidine in the water body, and other conditions are the same.

Control group five (CuFeS)₂PMS): with CuFeS₂Activated potassium hydrogen Peroxymonosulfate (PMS) is used for treating sulfadimidine in the water body, and other conditions are the same.

Control group six (CuFeS)₂/H₂O₂): with CuFeS₂Activated hydrogen peroxide (H)₂O₂) And (3) treating the sulfamethazine in the water body under the same other conditions.

Control group seven (CuFeS)₂): addition of CuFeS only₂And (3) treating the sulfamethazine in the water body under the same other conditions.

Control group eight (SPC): only SPC is added to treat sulfamethazine in the water body, and other conditions are the same.

In this example, CuFeS was used₂The preparation method comprises the following steps:

(1.1) adding 10mmol of CuCl and FeCl₃ ^.6H₂O is simultaneously dissolved in 57mL of ultrapure water and is fully and uniformly mixed by mechanical stirring.

(1.2) to the mixed solution in (1.1) above, 20mmol of (NH) was added₄)₂And (5) continuously mechanically stirring the S solution for 30min to fully and uniformly mix the S solution and the S solution to form black precipitates.

(1.3) transferring the mixed solution in the step (1.2) into a 100mL polytetrafluoroethylene reaction kettle inner container, carrying out hydrothermal reaction for 10h at 200 ℃, cooling the reaction solution to room temperature, washing with ultrapure water and ethanol, carrying out suction filtration to remove impurities, and drying in an air-blast drying oven at 60 ℃ for 12h to obtain CuFeS₂。

In this example, FeS was used₂The preparation method comprises the following steps:

(2.1) adding 10mmol of FeCl at room temperature₂·4H₂O was dissolved in 80mL of ethylene glycol, and then 30mmol of thiourea was added to the solution, and further mechanically stirred for 30min to mix it uniformly.

(2.2) transferring the mixed solution in the step (2.1) into a 100mL polytetrafluoroethylene reaction kettle inner container, and reacting for 12h at 160 ℃. After the reaction solution is cooled to room temperature, washing and filtering the reaction solution by using ultrapure water and ethanol to remove impurities, and then drying the reaction solution for 12 hours in a blast drying oven at the temperature of 80 ℃ to obtain FeS₂。

In this embodiment, the adopted method for preparing CuS includes the following steps:

(3.1) adding 10mmol of Cu (NO) at room temperature₃)₂·3H₂O was dissolved in 80mL of ethylene glycol, and then 30mmol of thiourea was added to the solution, and further mechanically stirred for 30min to mix it uniformly.

(3.2) transferring the mixed solution in the step (3.1) into a 100mL polytetrafluoroethylene reaction kettle inner container, and reacting for 12h at 160 ℃. And after the reaction solution is cooled to room temperature, washing and filtering the reaction solution by using ultrapure water and ethanol to remove impurities, and then drying the reaction solution in a forced air drying oven at the temperature of 80 ℃ for 12 hours to obtain CuS.

In this example, CuFeO was used₂The preparation method comprises the following steps:

(4.1) adding 15mmol of Cu (NO)₃)₂·3H₂O and Fe (NO)₃)₃·9H₂O is simultaneously dissolved in 60mL of ultrapure water and is fully and uniformly mixed by mechanical stirring.

(4.2) to the mixed solution of (4.1) above, 5.0g of NaOH and 5mL of ethylene glycol were added, followed by vigorous mechanical stirring for 60min to mix the three well.

(4.3) transferring the mixed solution in the step (4.2) into a 100mL polytetrafluoroethylene reaction kettle liner, and carrying out hydrothermal reaction for 24h at 180 ℃. Cooling the generated precipitate to room temperature, washing the precipitate to neutrality by using ultrapure water and ethanol, and drying the precipitate in a forced air drying oven at 80 ℃ for 12 hours.

In the embodiment, in the process of mechanical stirring treatment of a constant-temperature water bath, sampling is performed at regular time, a sample is filtered through a 0.22-micron water-phase filter membrane, and then the concentration of the residual sulfadimidine in the water sample is determined by using a high performance liquid chromatograph. The removal rate of sulfadimidine was calculated from the change in the concentration of sulfadimidine in the solution before and after the treatment, and the results are shown in fig. 1.

Fig. 1 is a comparison graph of the removal effect of sulfamethazine in a water body under different treatment systems in example 1 of the present invention. As can be seen from fig. 1: when CuFeO is used₂CuS and FeS₂When SPC was activated, the SMT removal rates were 70.4%, 28.8%, and 29.9%, respectively, compared to CuFeS₂More efficient activation of SPC, i.e., CuFeS₂The removal effect of the/SPC system on the sulfadimidine is optimal, the system is obviously higher than other three systems of transition metal material activated SPC, and the removal rate of pollutants can reach 86.4% within 45 min. CuFeS₂The advantages of activating SPC are mainly due to the possible synergistic effect between Cu and Fe, and the substitution of O with S with more electronegativity favors the cycling of the metal redox couple, thus CuFeS is finally selected in the present invention₂As a catalyst to activate SPC to treat bodies of water containing sulfadimidine.

Meanwhile, as can be seen from FIG. 1, when CuFeS is used₂To activate PS, PMS, H₂O₂The SMT removal rate in 45min is respectively 59.6 percent, 80.2 percent and 62.0 percent, which is lower than that of CuFeS₂The effect of sulfamethazine removal in SPC system. CuFeS₂The superiority of the/SPC system is mainly due to the efficient formation of different oxidizing actives under neutral conditions, while the other CuFeS₂Peroxide systems tend to be more efficient at removing target contaminants under acidic conditions. In addition, CuFeS₂the/SPC system also effectively avoids leaching of excess metal ions, maintains the pH of the treated effluent neutral, and the main end product of SPC is usually CO with no toxic effect₂、H₂O and Na₂CO₃. Thus, SPC is finally selected as the oxidant to cooperate with CuFeS in the invention₂Treating water containing sulfamethazine.

Example 2

A method for removing antibiotics in water body by using chalcopyrite activated percarbonate, specifically a method for removing antibiotics in water body by using CuFeS₂And sodium percarbonate to treat the sulfamethazine water body, comprising the following steps:

respectively adding CuFeS according to the addition amount of 0.5g/L and 0.8mmol/L₂And adding Sodium Percarbonate (SPC) into sulfadimidine water bodies with initial pH values of 3.1, 4.0, 5.81, 7.1 and 9.0 (the initial concentrations of sulfadimidine in the water bodies are all 5mg/L), placing the obtained reaction system in a digital display constant temperature water bath kettle for degradation reaction, and uniformly mixing the obtained reaction system with an electric mechanical stirrer in the degradation reaction process, wherein the constant temperature treatment temperature of the water body is 25 ℃, the mechanical stirring rotation speed is 250rpm, and the treatment time is 45min, thereby completing the removal of the sulfadimidine in the water body.

Control group: firstly adding Sodium Percarbonate (SPC), adjusting the pH value of sulfamethazine water body to 3.15, 5.81, 7.1, 9.0 and 10.54, and further adding CuFeS₂Other conditions are the same.

In the embodiment, in the process of mechanical stirring treatment of a constant-temperature water bath, sampling is performed at regular time, a sample is filtered through a 0.22-micron water-phase filter membrane, and then the concentration of the residual sulfadimidine in the water sample is determined by using a high performance liquid chromatograph. The removal rate of sulfadimidine was calculated from the change in the concentration of sulfadimidine in the solution before and after the treatment, and the results are shown in fig. 2 and 3.

FIG. 2 shows the simultaneous reaction of CuFeS in example 2 of the present invention₂And the comparative graph of the removal effect of the sulfadimidine when the sodium percarbonate is added into water bodies with different pH values. As can be seen from FIG. 2, since SPC is a strong base and weak acid salt and has a buffering action, the corresponding CuFeS was added to SPC in an amount of 0.8mmol/L₂The practical working pH value of the/SPC system can be maintained between 7.1 and 9.50, namely the reaction medium can be maintained in neutral and alkaline environments, the degradation of the SMT is facilitated in the neutral reaction medium (pH 7.1), and the initial pH value of the corresponding wastewater is 3.1.

FIG. 3 is a graph showing the effect of sulfadimidine removal after sodium percarbonate is added to adjust the pH of the water in example 2 of the present invention. As can be seen from FIG. 3, the removal efficiency of SMT was only 28.4% except that the initial pH was 10.54, and CuFeS was₂the/SPC system can obtain excellent SMT removal effect (75.8-100%) in the studied pH range (3.1-9.0), which indicates that CuFeS₂The pH of the/SPC system is widely applicable, but the buffer effect of the SPC on the reaction solution is lost under the pH adjusting operation condition, so that excessive metal ions Fe and Cu are leached out. Comprehensively considering the post-treatment cost and CuFeS of the balanced acidified effluent₂The invention is used for adjusting the initial pH value of the treated water body containing the sulfoamidodimethylpyrimidine before adding SPC.

As is clear from the results in FIGS. 1 to 3, the present invention utilizes CuFeS₂Activated percarbonate due to CuFeS₂The combined action of reducing substances existing on the surface, such as sulfur substances, Cu (I) and Fe (III), and superoxide radicals existing in the reaction system can accelerate CuFeS₂The redox cycling of the surface Fe species allows for sustained and efficient activation of percarbonate, producing a variety of reactive species with oxidizing capabilities, including^·OH、CO₃ ^·-、O₂ ^·-To be provided with¹O₂The sulfadimidine in the water body is attacked, and the aim of efficiently removing the sulfadimidine in a neutral aqueous medium can be achieved. CuFeS as compared to its corresponding single metal sulfides and metal oxides₂Exhibits more excellent ability to activate SPC. Similarly, the method is similar to the conventional CuFeS₂Method for activating peroxide, CuFeS₂The pollutant removing effect in the SPC system is optimal, the used sodium percarbonate has low price, safety and stability and easy storage and transportation, and the final decomposition product has no microbial toxic effect. In addition, the use of sodium percarbonate can not only effectively avoid the problem of acidification of treated effluent, but also greatly reduce the cost of wastewater treatment, but also ensure that CuFeS is used₂The pH of the/SPC system is used in a wider range. The invention overcomesThe existing advanced oxidation technology for activating peroxide by metal sulfide has the defect of non-ideal effect on treating target pollutants in water under neutral and alkaline conditions. Meanwhile, the advanced oxidation water treatment system constructed by the invention greatly avoids the problem of secondary pollution possibly caused by leaching of excessive toxic metal ions in the process of activating peroxide by the transition metal catalyst. Therefore, the method for removing the sulfamethazine in the water body has the advantages of simple process, short reaction time, good removal effect, wide pH application range, environmental friendliness and the like, and has wide application prospect.

The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.