CN112520834A - Method for degrading iodo-substituted drugs by activating sulfite system - Google Patents
Method for degrading iodo-substituted drugs by activating sulfite system Download PDFInfo
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- CN112520834A CN112520834A CN202011248149.3A CN202011248149A CN112520834A CN 112520834 A CN112520834 A CN 112520834A CN 202011248149 A CN202011248149 A CN 202011248149A CN 112520834 A CN112520834 A CN 112520834A
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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
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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
- C02F2101/12—Halogens or halogen-containing compounds
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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 discloses a method for degrading iodo-substituted drugs by activating a sulfite system. The specific operation is as follows: respectively adding transition metal sulfide and sulfite into the water body polluted by the iodophor, and continuously stirring. The invention utilizes the property that transition metal sulfide reacts with sulfite to generate strong oxidative sulfate radical free radical, thereby achieving the purpose of quickly degrading iodo-substituted drugs in polluted water. The transition metal sulfide used in the invention has the advantages of less leaching amount of transition metal ions, wide applicable pH value range, high electron transfer efficiency, good stability and the like, can be used as an environment-friendly heterogeneous activator to promote the generation of sulfate radicals, and provides an effective treatment method for solving the problem of low degradation efficiency of iodophors.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a method for degrading iodomedicine by using an activated sulfite system.
Background
Iodine-containing drugs are used as an important drug micro-pollutant, and the environment is threatened by frequent detection and difficult degradability in water bodies around the world. Advanced oxidation technologies based on sulfate radicals (SR-AOPs) are reported as a water advanced treatment technology that can efficiently generate strongly oxidizing sulfate radicals for the degradation of iodophores. The sulfate radical has the advantages of higher oxidation-reduction potential (2.5-3.1V), higher activity, good selectivity and the like; and sulfate radical can react in a wide pH range, has a long half-life (30-40 mus), and has a high reaction rate with contaminants (10)6-109M-1s-1) The reaction is less affected by aqueous background substances, and the like. Therefore, advanced oxidation technologies based on sulfate radicals have a wide prospect of development.
At present, precursors of sulfate radicals are mainly persulfates. For example, CN201811448685.0 discloses a method for removing iodo-based X-ray contrast agent in water, comprising the steps of: adding an oxidant: adding sodium persulfate into the water to be treated to ensure that the concentration of the sodium persulfate in the water is 23.8-71.4 mg/L; ultraviolet light irradiation: and (3) irradiating the water to be treated with the oxidant for 5-10 min under ultraviolet rays. The invention can reduce ICM concentration in water by more than 87%, and is less influenced by pH change, and the products generated by the reaction are mainly sulfate ions and iodate ions. CN201610663708.4 discloses a water treatment method for controlling iodo disinfection byproducts by using persulfate to catalyze ozone to oxidize refractory iodinated organic matters: and (3) introducing ozone into the ozone contact reactor, adding a persulfate catalyst under the stirring condition, and stirring for reaction treatment to obtain the treated water body. CN201710050369.7 discloses a water treatment method for in situ control of iodo by-products in chloramine disinfection process by monopersulfate: when chloramine is added into water to be treated for disinfection treatment, monopersulfate solution is added and stirred, iodine ions are oxidized into hypoiodic acid by utilizing the oxidability of monopersulfate, and the hypoiodic acid is further oxidized into nontoxic and harmless iodate, so that the control of the organic matter substituted by iodine is completed. The defects of the invention are as follows: the cost of the oxidant persulfate is high, and the activation of the persulfate by additional energy can increase the equipment investment and the operation cost.
Disclosure of Invention
The invention provides a novel solution for removing iodo-substituted drugs by a transition metal sulfide activated sulfite system in order to solve the problem of efficient degradation of the iodo-substituted drugs.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for degrading iodo-substituted drugs by activating a sulfite system comprises the following steps:
1) respectively adding transition metal sulfide and sulfite into a polluted water body, then fully stirring for reaction, activating the sulfite through the transition metal sulfide to generate strong-oxidative sulfate radicals, and quickly degrading iodomedicine; the concentration of the sulfite is 250-1500 mu M; the dosage of the transition metal sulfide is 0.02g/L-1.5 g/L; stirring for 20-40 min;
2) recovering the unreacted transition metal sulfide, said recovering being by physical means.
Preferably, the physical means recovery comprises filtering the reaction solution, or the transition metal sulfide is placed in a vessel including a filter in advance, and then the filter is recovered.
Preferably, the concentration of the sulfite is 500 μ M to 1000 μ M.
Preferably, the dosage of the transition metal sulfide is 0.05g/L to 0.5 g/L.
Preferably, the time for the reaction is stirred sufficiently for 30 to 35 min.
Preferably, the pH value of the polluted water body is 6-10.
Preferably, H is used2SO4And regulating the pH value of the polluted water body with NaOH.
Preferably, the iodo-substituted drugs in step (1) include several common iodo-substituted X-ray contrast agents (iopromide, iohexol, iopamidol, iomeprol, diatrizoate, etc.); further preferably, iohexol is selected as the target contaminant.
Preferably, the transition metal sulfide described in step (1) is any one of copper sulfide, cobalt sulfide, manganese sulfide, iron sulfide, and the like.
Preferably, the sulfite in step (1) is any one or more of potassium sulfite/sodium sulfite/calcium sulfite/magnesium sulfite.
The water containing the iodine-substituted drugs can be drinking water, tap water, underground water, sewage or industrial wastewater. In the practical application process, the proportion of the added reagent can be adjusted according to water quality parameters and water quality requirements, so as to achieve the purpose of efficiently degrading the iodomedicine.
The invention uses sulfite rather than persulfate with lower cost. By adopting transition metal ions, sulfite can be effectively activated to generate sulfate radical, thereby achieving the purpose of degrading pollutants. However, the direct addition of transition metal ions causes secondary pollution to water, and thus the application of such a homogeneous system is limited. In order to solve the problem, the invention adopts a method of respectively adding transition metal sulfide and sulfite, then fully stirring and reacting to construct heterogeneous activated sulfite to generate sulfate radical, and finally filtering and recovering the transition metal sulfide, so that the recovered transition metal sulfide can be further recycled besides no secondary pollution to water.
Compared with the prior art, the method provided by the invention has the advantages of cost saving, environmental friendliness, no secondary pollution, high recovery rate of the activating agent, good degradation effect under the conditions of normal temperature and wider pH value, simplicity in operation and suitability for degradation of iodomedicine in the polluted water body. In addition, the transition metal sulfide has double active sites of transition metal and sulfur, so that the material has high electron transfer efficiency, is simple and easy to obtain and recover, and is an environment-friendly material. In the invention, transition metal sulfide is adopted to activate sulfite to generate sulfate radical to efficiently degrade iodo-substituted drugs, and the system can achieve higher degradation effect within 30 min.
Drawings
FIG. 1 is a graph showing the effect of different cobalt sulfide dosages on the efficiency of iohexol degradation in accordance with example 1 of the present invention.
FIG. 2 is a graph showing the effect of different sulfite concentrations on the degradation of iohexol in example 2 of the present invention.
FIG. 3 is a graph showing the degradation effect of iohexol at different concentrations in example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples:
example 1
As a method for degrading iodine medicaments by activating a sulfite system, the activator selects transition metal sulfides such as copper sulfide, cobalt sulfide, manganese sulfide, iron sulfide and the like, potassium sulfite/sodium/calcium/magnesium is a precursor of sulfate radicals, and a micro-pollutant selects iodine X-ray contrast agent iohexol.
Firstly, respectively adding 0.001g-0.05g of cobalt sulfide into a water body to be treated, wherein the iodine-containing medicament is iohexol; then, adding sulfite to start reaction, and starting timing; samples were taken at 0, 0.5, 1, 3, 5, 10, 20 and 30min, respectively, and the samples were passed through a 0.22 μm filter to quench the active radicals in the reaction solution, and analyzed for iohexol concentration by ultra high performance liquid chromatography.
The effect of different cobalt sulphide doses on the efficiency of iohexol degradation is shown in figure 1, with the abscissa representing the cobalt sulphide dose (g/L) and the ordinate representing the iohexol degradation (C/C)0). In this example, the dosage of cobalt sulfide was optimized for iohexol degradation at concentrations of 0.01, 0.02, 0.05, 0.1, 0.2, and 0.5g/L, respectively, where the sulfite concentration was 500. mu.M, the iohexol concentration was 10. mu.M, and the pH was 8. The results show that: the dosage of cobalt sulfide is increased, cobalt and sulfur active sites participating in the reaction are directly increased, the contact surface with sulfite is increased, more sulfate radicals can be generated, and the rapid degradation of iohexol is promoted. However, with the increasing dosage of cobalt sulfide, the sulfite concentration which can rapidly react with cobalt sulfide is constant, so that the degradation effect of iohexol tends to be smooth, and finally the system can reach about 90% of iohexol degradation efficiency.
Example 2
This embodiment differs from embodiment 1 in that: the concentration of the cobalt sulfide is optimized in the embodiment 1, and the concentration of the cobalt sulfide is finally selected to be 0.05 g/L; in this embodiment, the concentration of sulfite is in the range of 100-1000. mu.M.
The effect of different sulfite concentrations on the efficiency of iohexol degradation is shown in FIG. 2, with the concentration of sulfite (. mu.M) on the abscissa and the degradation of iohexol (C/C) on the ordinate0). In this example, the concentration of sulfite was optimized to degrade iohexol at concentrations of 100, 250, 500, 750, and 1000 μ M, respectively, wherein the dosage of cobalt sulfide was 0.05g/L, the concentration of iohexol was 10 μ M, and the pH was 8. The results show that: the increase of the concentration of the sulfite, namely the increase of the concentration of sulfite ions which can participate in the reaction in the system can promote the generation of sulfate radicals in the system; however, the cobalt sulfide concentration in the system is 0.05g/L, namely the active site is constant, so that the degradation effect of the iohexol is not improved by excessive sulfite concentration, and finally the system can achieve about 90% of the iohexol degradation efficiency.
Example 3
This embodiment differs from embodiment 2 in that: the concentration of sulfite was finally selected to be 500 μ M by optimization of the sulfite concentration in example 2; in this example, the concentration of iohexol ranges from 2 to 10. mu.M.
The effect of different iohexol concentrations on the efficiency of iohexol degradation is shown in FIG. 3, with the abscissa representing the concentration of iohexol (. mu.M) and the ordinate representing the degradation of iohexol (C/C)0). In this example, iohexol was degraded at different concentrations, 2, 4, 6, 8, 10 μ M, wherein the dosage of cobalt sulfide was 0.05g/L, the concentration of sulfite was 10 μ M, and the pH was 8. The results show that: when the concentration of iohexol is 2-8 mu M, the degradation effect of the system on iohexol can reach 100%; when the concentration of the pollutants is 10 mu M, the degradation efficiency is 89 percent. The system has obvious degradation effect on the iohexol, and if the concentrations of the cobalt sulfide and the sulfite are properly increased, the iohexol in the polluted water body can be completely degraded.
The above description is only a preferred embodiment used in the process of the present invention, and no determination of the optimal dosage has been made, so the scope of the practice of the present invention should not be limited accordingly. The embodiments are described in sufficient detail to enable those skilled in the art to make and use the invention. Therefore, the present invention is not limited to the above embodiments, and equivalent changes and modifications made according to the claims and the contents of the specification of the present invention should be covered by the present invention.
Claims (10)
1. A method for degrading iodo-substituted drugs by activating a sulfite system comprises the following steps:
1) respectively adding transition metal sulfide and sulfite into a polluted water body, then fully stirring for reaction, activating the sulfite through the transition metal sulfide to generate strong-oxidative sulfate radicals, and quickly degrading iodomedicine; the concentration of the sulfite is 250-1500 mu M; the dosage of the transition metal sulfide is 0.02g/L-1.5 g/L; stirring for 20-40 min;
2) recovering the unreacted transition metal sulfide, said recovering being by physical means.
2. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the physical means recovery comprises filtering the reaction solution, or putting the transition metal sulfide in a filter screen in advance, and then recovering the filter screen.
3. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the concentration of the sulfite is 500-1000 μ M.
4. The method for degrading iodo drugs by using the system of activated sulfite according to claim 3, wherein: the dosage of the transition metal sulfide is 0.05g/L-0.5 g/L.
5. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the time for fully stirring and reacting is 25-35 min.
6. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the pH value of the polluted water body is 6-10.
7. The method for activating the sulfite system to degrade iodo-substituted drugs according to claim 6, wherein: by means of H2SO4And regulating the pH value of the polluted water body with NaOH.
8. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the iodo-compound comprises an iodo-X-ray contrast agent, and the iodo-X-ray contrast agent comprises at least one of iopromide, iohexol, iopamidol, iomeprol and diatrizoate.
9. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the transition metal sulfide comprises at least one of cuprous sulfide, copper sulfide, cobalt sulfide, manganese sulfide and iron sulfide.
10. The method for degrading iodo drugs by using the activated sulfite system according to claim 1, wherein: the sulfite is at least one of potassium sulfite/sodium sulfite/calcium sulfite/magnesium sulfite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115925086A (en) * | 2022-12-02 | 2023-04-07 | 重庆大学 | Method for degrading organic matters in wastewater |
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| CN109231565A (en) * | 2018-10-24 | 2019-01-18 | 辽宁大学 | A method of degradation waste water containing Iopromide |
| CN110272110A (en) * | 2019-07-08 | 2019-09-24 | 华侨大学 | A kind of iodo drug degradation method based on MOF template |
| CN110862130A (en) * | 2019-12-05 | 2020-03-06 | 广州大学 | Method for disinfecting water and degrading iodo-contrast agent in water |
| CN110885145A (en) * | 2018-09-11 | 2020-03-17 | 华中科技大学 | Method for synchronously removing pollutants in water body and controlling generation of bromine-containing byproducts |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006192378A (en) * | 2005-01-14 | 2006-07-27 | Idemitsu Kosan Co Ltd | Hardly decomposable substances-containing water treatment method |
| CN110885145A (en) * | 2018-09-11 | 2020-03-17 | 华中科技大学 | Method for synchronously removing pollutants in water body and controlling generation of bromine-containing byproducts |
| CN109231565A (en) * | 2018-10-24 | 2019-01-18 | 辽宁大学 | A method of degradation waste water containing Iopromide |
| CN110272110A (en) * | 2019-07-08 | 2019-09-24 | 华侨大学 | A kind of iodo drug degradation method based on MOF template |
| CN110862130A (en) * | 2019-12-05 | 2020-03-06 | 广州大学 | Method for disinfecting water and degrading iodo-contrast agent in water |
Cited By (1)
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| CN115925086A (en) * | 2022-12-02 | 2023-04-07 | 重庆大学 | Method for degrading organic matters in wastewater |
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