CN112624413A - Method for simultaneously converting tetracycline organic molecules and trivalent arsenic - Google Patents
Method for simultaneously converting tetracycline organic molecules and trivalent arsenic Download PDFInfo
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- CN112624413A CN112624413A CN202011507958.1A CN202011507958A CN112624413A CN 112624413 A CN112624413 A CN 112624413A CN 202011507958 A CN202011507958 A CN 202011507958A CN 112624413 A CN112624413 A CN 112624413A
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- tetracycline
- trivalent arsenic
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/722—Oxidation by peroxides
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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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
A method for simultaneously converting tetracycline organic molecules and trivalent arsenic is characterized in that Fe is added into wastewater to be treated in which tetracycline and trivalent arsenic pollution simultaneously exist3+And H2O2Reduction of Fe with tetracycline3+Produced Fe2+Decomposition of H2O2Generates OH, and realizes the efficient synergistic conversion of tetracycline and trivalent arsenic. The method solves the problems that the traditional Fenton reaction needs a strong acid environment and a large amount of Fe is added2+By adding a small amount of Fe3+At lower H2O2The tetracycline is removed and the trivalent arsenic is converted at the same time within a wider pH range.
Description
Technical Field
The invention belongs to the field of organic matter-heavy metal composite polluted water treatment, and particularly relates to a method for simultaneously converting tetracycline organic molecules and trivalent arsenic.
Background
The tetracycline antibiotic is a broad-spectrum antibiotic, and is widely applied to livestock and poultry breeding, preventing and controlling diseases and promoting animal growth. Only part of tetracycline entering the organism can be absorbed and utilized, about 70-90% of tetracycline enters the environment along with excrement, and negative effects are caused to aquatic and terrestrial organisms. The long-term antibiotic residue results in the generation of antibiotic resistance genes, and has higher ecological environment risk.
The organic arsenic preparations such as roxarsone, arsonic acid and the like have the effects of resisting bacteria and parasites and stimulating the growth of animals, can improve the nutrition of animal skins, make the skins glossy and the furs of the animals glossy and improve the quality, and are common feed additives for livestock and poultry breeding industry. The organic arsenic preparation is difficult to absorb and degrade in animal bodies, most of the organic arsenic preparation enters soil or water along with excrement, and is converted into inorganic arsenic with higher mobility and toxicity through biological or non-biological reaction.
Intensive and large-scale production of livestock and poultry breeding industry ensures that feed additives such as tetracycline antibiotics, organic arsenic preparations and the like are used in large quantities, wherein a small amount of the feed additives are absorbed by animals, and most of the feed additives are discharged out of bodies along with excrement, so that high accumulation amount exists in livestock and poultry excrement and wastewater. For example, sampling investigation of livestock manure in Shanghai multi-livestock farms shows that the concentration of tetracycline is as high as 2.6-617.2 mg-kg−1The arsenic concentration is as high as 4.54-24.66 mg/kg−1. How to rapidly and efficiently remove the tetracycline-arsenic composite pollution in the livestock wastewater is of great concern.
With OH (E)0=2.80eV), has high oxidation activity and no selectivity, and is often used for removing pollutants from complex systems. Fe is required for the conventional Fenton reaction2+As a catalyst, the reaction needs to be performed at about pH =3, and Fe2+Is oxidized into Fe3+The reduction is difficult to carry out, and the reaction is limited. It has been reported that some organic acid molecules such as oxalic acid, citric acid, protocatechuic acid, etc. can react with Fe3+Form a Fenton-like system, and generate Fe in situ within a wider pH range2+Decomposition of H2O2OH is produced. The tetracycline molecule contains-OH and-NH2Isofunctional group, for Fe3+Also has certain complexing and reducing capability. If the reaction of the two is utilized to generate Fe in situ2+Decomposition of H2O2Generation of OHThe method can be used for simply and efficiently treating tetracycline-arsenic composite pollution in the water body.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a method for converting tetracycline organic molecules and trivalent arsenic, which can simultaneously convert tetracycline antibiotic molecules and trivalent arsenic in livestock wastewater.
The technical scheme is as follows: application of a composition of ferric iron and hydrogen peroxide in treating wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously.
The method for treating the wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously by using the composition of ferric iron and hydrogen peroxide comprises the following specific steps: (1) adjusting the pH value of the wastewater containing tetracycline organic molecules and trivalent arsenic to 4.5-7.5; (2) adding Fe into the wastewater after the pH is adjusted3+Mixing until the concentration is 20-70 μ M; (3) adding H into the mixed solution obtained in the step 22O2To a concentration of 0.15 to 0.25mM, and the reaction was stirred well.
Preferably, the concentration of the tetracycline-based organic molecule is 50 μ M.
Preferably, the concentration of trivalent arsenic is 50. mu.M.
Preferably, the reaction system has a pH of 5.5.
Preferably, Fe is as defined above3+The concentration of (3) was 50. mu.M.
Preferably, the above-mentioned H2O2Is 0.2 mM.
Preferably, the reaction time is 90 min.
The tetracycline organic molecule is at least one of oxytetracycline or chlorotetracycline, and the trivalent arsenic is arsenite.
The composition for treating the wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously contains trivalent iron and hydrogen peroxide as effective components.
Has the advantages that: (1) the invention provides a method for efficiently converting trivalent arsenic by using tetracycline organic molecules to promote Fenton-like reaction in situThe method can simultaneously and efficiently remove the combined pollution of tetracycline organic molecules and trivalent arsenic in the wastewater; (2) the method provided by the invention is simple to operate, and only Fe needs to be added into the wastewater containing tetracycline organic molecules and trivalent arsenic3+And H2O2The high-efficiency synergistic conversion of the tetracycline and the trivalent arsenic can be realized under the conditions of normal temperature and normal pressure; (3) the method provided by the invention has low treatment cost, and only needs to add a small amount of Fe3+And H2O2Using tetracycline organic molecules with Fe3+Complexing reaction to generate Fe in situ2+To induce Fenton reaction without adding extra Fe2+(ii) a (4) The method provided by the invention is less influenced by environmental factors, and has good removal effect in a wider pH range compared with the traditional Fenton reaction; (5) the method provided by the invention is green and efficient, and H is obtained after the reaction is finished2O2Can be basically completely consumed, and a small amount of Fe3+Exists in a free state or a complex state and is harmless to the environment.
Drawings
FIG. 1 is Fe alone3+Or H2O2And the removal effect of the combination of the tetracycline and the trivalent arsenic is compared;
FIG. 2 is a graph comparing the effectiveness of the method of the present invention in removing tetracycline and trivalent arsenic with a conventional Fenton system;
FIG. 3 is a graph of the effect of different pH on tetracycline and arsenic removal;
FIG. 4 shows different Fe3+The influence of the addition amount on the removal effect of tetracycline and trivalent arsenic;
FIG. 5 shows a case of a variation H2O2The effect of the amount of the added tetracycline and the trivalent arsenic on the removal effect.
Detailed Description
The invention is further illustrated by the following examples to illustrate the salient features of the invention, which are given by way of illustration only and are not to be construed as being limited by the following examples.
The normal temperature and pressure in the invention means 20 ℃ and one standard atmospheric pressure.
Example 1:
in the embodiment, an environment-friendly method for effectively and synergistically converting tetracycline and trivalent arsenic comprises the following specific implementation steps:
(1) adjusting the pH value of the wastewater to be treated containing tetracycline and trivalent arsenic pollutants to 5.5;
(2) adding 50 mu M Fe into the wastewater after the pH adjustment3+Or 0.2mM H2O2Or simultaneously adding 50 mu M Fe3+Or 0.2mM H2O2Mixing uniformly;
(3) and (3) fully stirring the mixed solution obtained in the step (2) to react for 90 min.
In this example, Fe alone3+And H2O2And the effect on the conversion of tetracycline and trivalent arsenic is not obvious. Using tetracycline and Fe3+Reaction, in situ generation of Fe2+Decomposition of H2O2And high-oxidizing OH is generated, and the efficient synergistic conversion of tetracycline and trivalent arsenic can be realized. The results are shown in FIGS. 1(a) and 1(b), and Fe3+/ H2O2The combination realizes the removal of more than 95 percent of tetracycline and trivalent arsenic in the environment of normal temperature and pressure and near neutrality.
Example 2:
the implementation comprises the following specific implementation steps:
(1) adjusting the pH value of the wastewater to be treated containing tetracycline and trivalent arsenic pollutants to 5.5;
(2) after the pH adjustment, 50. mu.M Fe was added to the wastewater3+Or Fe2+Mixing uniformly;
(3) adding 0.2mM H to the mixture obtained in step 22O2The reaction was stirred well for 90 min.
In this example, in situ generated or dosed Fe is utilized2+Decomposition of H2O2And high-oxidative OH is generated, and the efficient synergistic conversion of tetracycline and trivalent arsenic is realized. The results are shown in FIG. 2(a),Shown in FIG. 2(b), Fe3+With Fe2+The similar catalytic effect realizes the removal of more than 95 percent of tetracycline and trivalent arsenic in the environment of normal temperature, normal pressure and near neutrality. Fe3+Compared with Fe2+Low cost, convenient storage and more suitability for wastewater treatment.
Example 3:
this embodiment is substantially the same as embodiment 2, except that: in the step (1), the pH ranges of the wastewater systems are different. In this example, the pH of the wastewater to be treated was adjusted to 4.5, 5.5, 6.5 and 7.5, respectively, and 50. mu.M Fe was added in step (2)3+And treating wastewater containing tetracycline and trivalent arsenic.
As shown in FIG. 3, tetracycline and trivalent arsenic were removed to some extent at a pH of 4.5 to 7.5. Wherein, the degradation rate of the tetracycline is relatively low at pH 4.5 or 7.5, respectively 51.2% and 58.7%, and the degradation rate is more than 92% at pH 5.5 or 6.5. The removal rate of trivalent arsenic can reach more than 97% within the pH range of 4.5-6.5, but is relatively low, only 28.7%, when the pH is 7.5.
Example 4:
this embodiment is substantially the same as embodiment 2, except that: in step (2), Fe3+The dosage is different. In this example, Fe3+The dosage of (A) is 10 mu M, 20 mu M, 50 mu M, 100 mu M and 200 mu M respectively, and the wastewater containing tetracycline and trivalent arsenic is treated.
The results are shown in FIG. 4, with Fe3+The dosage is increased from 10 mu M to 50 mu M, the removal rates of tetracycline and trivalent arsenic are increased, and the maximum removal rates are 91.9 percent and 96.2 percent respectively. Rear Fe3+The removal efficiency was slightly decreased when the concentrations were increased to 100. mu.M and 250. mu.M.
Example 5:
this embodiment is substantially the same as embodiment 2, except that: adding 50 mu M Fe in the step (2)3+In step (3), H2O2The dosage is different. In this embodiment, H2O2The amounts of (A) and (B) were 0.1mM, 0.2mM, 0.5mM, 1mM and 2mM, respectively, and wastewater containing tetracycline and trivalent arsenic was treated.
The results are shown in FIG. 5, with H2O2The dosage is increased from 0.1mM to 2mM, and the removal rate of tetracycline and trivalent arsenic is increased, wherein in H2O2When the adding amount is 0.2mM, 92% of tetracycline and 96% of trivalent arsenic can be removed; and at H2O2When the adding amount is 1mM, the complete removal of tetracycline and the removal of 97 percent of trivalent arsenic can be realized. Therefore, the removal effect and cost are comprehensively considered, H2O2The dosage was chosen to be 0.2 mM.
Claims (10)
1. Application of a composition of ferric iron and hydrogen peroxide in treating wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously.
2. The method for treating the wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously by using the composition of ferric iron and hydrogen peroxide is characterized by comprising the following specific steps of:
(1) adjusting the pH value of the wastewater containing tetracycline organic molecules and trivalent arsenic to 4.5-7.5;
(2) adding Fe into the wastewater after the pH is adjusted3+Mixing until the concentration is 20-70 μ M;
(3) adding H into the mixed solution obtained in the step 22O2To a concentration of 0.15 to 0.25mM, and the reaction was stirred well.
3. The method of claim 2, wherein: the concentration of the tetracycline organic molecules was 50 μ M.
4. The method of claim 2, wherein: the concentration of trivalent arsenic was 50. mu.M.
5. The method of claim 2, wherein: the pH of the reaction system was 5.5.
6. The method of claim 2, wherein: fe3+The concentration of (3) was 50. mu.M.
7. The method of claim 2, wherein: h2O2Is 0.2 mM.
8. The method of claim 2, wherein: the reaction time was 90 min.
9. The method of claim 2, wherein: the tetracycline organic molecule is at least one of oxytetracycline or chlorotetracycline, and the trivalent arsenic is arsenite.
10. The composition for treating wastewater containing tetracycline organic molecules and trivalent arsenic simultaneously is characterized in that the effective components are ferric iron and hydrogen peroxide.
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| CN202011507958.1A CN112624413A (en) | 2020-12-18 | 2020-12-18 | Method for simultaneously converting tetracycline organic molecules and trivalent arsenic |
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| CN202011507958.1A CN112624413A (en) | 2020-12-18 | 2020-12-18 | Method for simultaneously converting tetracycline organic molecules and trivalent arsenic |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114643276A (en) * | 2022-02-23 | 2022-06-21 | 青岛理工大学 | Method for in-situ remediation of arsenic and tetracycline hydrochloride contaminated soil by bacteria and application |
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2020
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| KR20070111602A (en) * | 2006-05-18 | 2007-11-22 | 조원기 | A pharmaceutical composition for colitis induced by pernicious enteric bacterium |
| WO2009011076A1 (en) * | 2007-07-13 | 2009-01-22 | Dowa Metals & Mining Co., Ltd. | Method of treating nonferrous smelting intermediate product containing arsenic |
| CN108059228A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of sulfamido antiseptic in removal livestock breeding wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114643276A (en) * | 2022-02-23 | 2022-06-21 | 青岛理工大学 | Method for in-situ remediation of arsenic and tetracycline hydrochloride contaminated soil by bacteria and application |
| CN114643276B (en) * | 2022-02-23 | 2024-03-08 | 青岛理工大学 | Method for in-situ remediation of arsenic and tetracycline hydrochloride contaminated soil by bacteria and application of method |
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Application publication date: 20210409 |