CN111825199A - Method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide - Google Patents
Method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide Download PDFInfo
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- CN111825199A CN111825199A CN202010553099.3A CN202010553099A CN111825199A CN 111825199 A CN111825199 A CN 111825199A CN 202010553099 A CN202010553099 A CN 202010553099A CN 111825199 A CN111825199 A CN 111825199A
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- calcium peroxide
- inorganic perovskite
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide, belonging to the technical field of sewage treatment. The method comprises the following steps: sequentially adding calcium peroxide and inorganic perovskite into a polluted water body containing refractory antibiotics, and carrying out shaking reaction for 24-48 h at the temperature of 15-30 ℃ by adopting a shaking table. The method provided by the invention degrades the refractory antibiotics in water by using inorganic free radicals generated by catalyzing calcium peroxide by inorganic perovskite, is simple and convenient to operate, can overcome the defect that the capability of activating calcium peroxide by transition metal salt is gradually reduced along with the pH trend of a reaction system towards alkalinity, and has a good oxidative degradation effect on the refractory antibiotics.
Description
Technical Field
The invention relates to a method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide, belonging to the technical field of sewage treatment.
Background
Antibiotics refer to a class of secondary metabolites which are produced by bacteria, fungi or other microorganisms in the life process, have anti-pathogen or other activities, can interfere or inhibit the survival of pathogenic microorganisms, and are widely used in the industries of medical treatment, livestock and poultry breeding and the like. In recent years, with the improvement of living standard of people, the production and use amount of antibiotics in China are increasing day by day. China is the biggest antibiotic producing country and the largest antibiotic using country in the world, and the usage amount of antibiotics in China is 16.2 million tons in 2013 all year round, and accounts for about half of the usage amount of antibiotics in the world. The use of a large amount of antibiotics leads the antibiotics to enter environmental media such as surface water, sediments and soil of sewage treatment plants, rivers and the like through various ways, and the types of the antibiotics which are detected frequently mainly comprise Sulfonamides (SAs), Quinolones (QNs), Macrolides (MLs) and Tetracyclines (TCs).
The calcium peroxide is commonly called solid hydrogen peroxide, is an environment-friendly material, is stable at normal temperature and is easy to store. One of the important properties is that the hydrogen peroxide and oxygen can be generated by the reaction with water, and the hydrogen peroxide and oxygen have the oxidation and oxygen release capabilities in a humid environment, so that the hydrogen peroxide and oxygen release agent is widely used in the industries of agriculture, breeding and the like and is also widely used in the field of environmental protection. For example, the oxygen supply agent is used as a remediation treatment agent in the riverway polluted bottom mud remediation process, and continuously supplies oxygen to the polluted bottom mud environment while removing organic pollutants through oxidation, so that the chemical and biological remediation effects of pollution treatment are improved. In the field of polluted soil remediation, organic pollutants in the soil are degraded and removed by multiple modes such as continuous chemical oxidation, physical adsorption and the like by adding the organic pollutants into a polluted soil medium. In the field of wastewater treatment, calcium peroxide can replace hydrogen peroxide to be used as an efficient oxidant to remove antibiotics which are difficult to degrade in water.
At present, soluble transition metal salt such as ferrous salt is usually adopted to catalyze calcium peroxide to generate hydroxyl radicals to improve the oxidative degradation effect of calcium peroxide on refractory antibiotics in water, but a common soluble transition metal catalyst generally has a better catalytic effect only when being used in an acidic system, and when the common soluble transition metal catalyst is added into a water body with calcium peroxide, the pH value of the system tends to be slightly alkaline along with the progress of degradation reaction, and the capacity of the transition metal salt for activating the calcium peroxide also gradually decreases along with the tendency of the pH value of the reaction system to be slightly alkaline, which means that the soluble transition metal salt is used for activating the calcium peroxide and cannot achieve a better oxidative degradation effect on the refractory antibiotics in water.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide, which degrades the refractory antibiotics in the water by using inorganic free radicals generated by catalyzing the calcium peroxide by the inorganic perovskite, has simple and convenient operation, can overcome the defect that the capability of activating the calcium peroxide by transition metal salt is gradually reduced along with the trend of pH of a reaction system to be alkaline, and has good oxidative degradation effect on the refractory antibiotics.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide comprises the following steps: sequentially adding calcium peroxide and inorganic perovskite into a polluted water body containing refractory antibiotics, and carrying out shaking reaction for 24-48 h at the temperature of 15-30 ℃ by adopting a shaking table.
Preferably, the ratio of the adding mass of the calcium peroxide to the mass of the refractory antibiotics in the water body is (10-20): 1.
Further preferably, the ratio of the adding mass of the calcium peroxide to the mass of the refractory antibiotics in the water body is (10-12): 1.
Preferably, the inorganic perovskite and the calcium peroxide are both added into the polluted water body in a powder form, and the adding mass ratio of the inorganic perovskite to the calcium peroxide is (0.2-3): 1.
Further preferably, the inorganic perovskite and the calcium peroxide are both added into the polluted water body in a powder form, and the adding mass ratio of the inorganic perovskite to the calcium peroxide is (0.5-1): 1.
Preferably, the content of the active ingredient of the calcium peroxide is 50-75%.
Preferably, the refractory antibiotic is one or a mixture of tetracycline, macrolide, sulfanilamide and quinolone.
Preferably, the rotating speed of the shaking table is set to be 100-200 r/min.
From the above description, it can be seen that the present invention has the following advantages:
(1) the method utilizes inorganic free radicals generated by catalyzing calcium peroxide by the inorganic perovskite to degrade the refractory antibiotics in water, has simple and convenient operation, mild reaction and high removal efficiency of the refractory antibiotics in the water body;
(2) according to the invention, the inorganic perovskite is adopted to replace the traditional ferrite, so that the pH range of the reaction system can be effectively widened, new pollution is not introduced into the perovskite, the activation efficiency of calcium peroxide is high, and the defect that the calcium peroxide activation capability of the transition metal salt is gradually reduced along with the pH trend of the reaction system towards alkalinity can be overcome;
(3) the invention utilizes the calcium peroxide as an oxidant, and compared with liquid hydrogen peroxide, the solid calcium peroxide has stable property and is easy to store, transport and operate.
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1
Taking 1L of a sewage water sample containing tetracycline, and determining the concentration of the tetracycline in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the tetracycline in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 24 hours and 36 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the tetracycline concentration in the water body by adopting a liquid chromatography after the reaction is finished. The results show that the removal rates of tetracycline in the water body after 24h and 36h of reaction respectively reach 89.1 percent and 92.0 percent.
Example 2
Taking 1L of macrolide-containing sewage water sample, and determining the concentration of macrolide in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to macrolide in a water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 24 hours and 36 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the concentration of macrolide in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rates of macrolide in the water body after 24h and 36h of reaction respectively reach 93.8 percent and 95.0 percent.
Example 3
Taking 1L of sewage water sample containing sulfanilamide, and determining the concentration of sulfanilamide in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the mass of sulfanilamide in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 24 hours and 36 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the sulfanilamide concentration in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rate of the sulfanilamide in the water body after 24 hours and 36 hours of reaction respectively reaches 84.8 percent and 87.8 percent.
Example 4
Taking 1L of a quinolone-containing sewage water sample, and determining that the concentration of quinolone in sewage is 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the mass of quinolone in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 24 hours and 36 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the concentration of quinolone in the water body by adopting a liquid chromatography after the reaction is finished. The results show that the removal rates of the quinolone in the water body after 24 hours and 36 hours of reaction respectively reach 90.5 percent and 95.8 percent.
Comparative example 1
Taking 1L of a sewage water sample containing tetracycline, and determining the concentration of the tetracycline in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the tetracycline in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 12 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the tetracycline concentration in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rate of the tetracycline in the water body after 12 hours of reaction is 85.2%.
Comparative example 2
Taking 1L of macrolide-containing sewage water sample, and determining the concentration of macrolide in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to macrolide in a water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 12 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the concentration of macrolide in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rate of macrolide in the water body after 12 hours of reaction is 90.8%.
Comparative example 3
Taking 1L of sewage water sample containing sulfanilamide, and determining the concentration of sulfanilamide in the sewage to be 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the mass of sulfanilamide in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively carrying out oscillation reaction for 12 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the sulfanilamide concentration in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rate of the sulfanilamide in the water body after 12 hours of reaction is 76.3%.
Comparative example 4
Taking 1L of a quinolone-containing sewage water sample, and determining that the concentration of quinolone in sewage is 1 mmol/L;
sequentially adding solid powder of calcium peroxide (the content of active ingredients is 75%) and solid powder of inorganic perovskite into a sewage water sample, wherein the mass ratio of the added calcium peroxide to the mass of quinolone in the water body is 15:1, the mass ratio of the added inorganic perovskite to the added calcium peroxide is 1:1, respectively oscillating and reacting for 12 hours at the temperature of 20 ℃ by adopting a shaking table with the rotating speed of 150r/min, and measuring the concentration of quinolone in the water body by adopting a liquid chromatography after the reaction is finished. The result shows that the removal rate of the quinolone in the water body after 12 hours of reaction is 81.6%.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (8)
1. A method for removing refractory antibiotics in sewage by using inorganic perovskite activated calcium peroxide is characterized by comprising the following steps: sequentially adding calcium peroxide and inorganic perovskite into a polluted water body containing refractory antibiotics, and carrying out shaking reaction for 24-48 h at the temperature of 15-30 ℃ by adopting a shaking table.
2. The method according to claim 1, wherein the ratio of the added mass of the calcium peroxide to the mass of the refractory antibiotic in the water body is (10-20): 1.
3. The method according to claim 2, wherein the ratio of the added mass of the calcium peroxide to the mass of the refractory antibiotic in the water body is (10-12): 1.
4. The method according to claim 1, wherein the inorganic perovskite and the calcium peroxide are added into the polluted water body in powder form, and the mass ratio of the inorganic perovskite to the calcium peroxide is (0.2-3): 1.
5. The method according to claim 4, wherein the inorganic perovskite and the calcium peroxide are added into the polluted water body in powder form, and the mass ratio of the inorganic perovskite to the calcium peroxide is (0.5-1): 1.
6. The method of claim 1, wherein the calcium peroxide has an active ingredient content of 50% to 75%.
7. The method of claim 1, wherein the refractory antibiotic is any one or a mixture of tetracycline, macrolide, sulfonamide, or quinolone.
8. The method according to claim 1, wherein the rotational speed of the rocking platforms is set to 100 to 200 r/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133202A1 (en) * | 2007-05-24 | 2010-06-03 | Universita' Degli Stkudi Di Salerno | Wastewater treatment by high efficiency heterogeneous photo-fenton process |
| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
| CN103785394A (en) * | 2012-10-30 | 2014-05-14 | 同济大学 | Preparation method and use of three-dimensional nano-perovskite-type composite heterogeneous Fenton catalyst |
| CN106040249A (en) * | 2016-06-20 | 2016-10-26 | 西安交通大学 | Perovskite catalytic persulfate, and preparation method and application thereof |
| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | A kind of catalyst and preparation method thereof for catalytic wet oxidation nitro-chlorobenzene waste water |
-
2020
- 2020-06-17 CN CN202010553099.3A patent/CN111825199A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133202A1 (en) * | 2007-05-24 | 2010-06-03 | Universita' Degli Stkudi Di Salerno | Wastewater treatment by high efficiency heterogeneous photo-fenton process |
| CN103785394A (en) * | 2012-10-30 | 2014-05-14 | 同济大学 | Preparation method and use of three-dimensional nano-perovskite-type composite heterogeneous Fenton catalyst |
| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
| CN106040249A (en) * | 2016-06-20 | 2016-10-26 | 西安交通大学 | Perovskite catalytic persulfate, and preparation method and application thereof |
| CN110075856A (en) * | 2019-05-21 | 2019-08-02 | 南京工业大学 | A kind of catalyst and preparation method thereof for catalytic wet oxidation nitro-chlorobenzene waste water |
Non-Patent Citations (2)
| Title |
|---|
| HANS F.STROO等: "《地下水氯代烃污染羽原位修复》", 31 March 2015, 北京：地质出版社 * |
| YULUN NIE等: "Enhanced Fenton-like degradation of refractory organic compounds by surface complex formation of LaFeO3 and H2O2", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
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