CN108855083B - Method for removing sulfonamides in water by activating peracetic acid with modified zeolite - Google Patents

Method for removing sulfonamides in water by activating peracetic acid with modified zeolite Download PDF

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CN108855083B
CN108855083B CN201810731624.9A CN201810731624A CN108855083B CN 108855083 B CN108855083 B CN 108855083B CN 201810731624 A CN201810731624 A CN 201810731624A CN 108855083 B CN108855083 B CN 108855083B
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water
reaction
sulfonamides
zeolite
peroxyacetic acid
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CN108855083A (en
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付永胜
汪诗翔
刘义青
张李
吴鹏
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Southwest Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • 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
    • 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
    • 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
    • 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
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Abstract

The invention discloses a method for removing sulfonamides in water by activating peracetic acid with modified zeolite, which comprises the following steps: s1, catalyst preparation: grinding artificial zeolite into fine powder, pickling, washing with water, drying, soaking in ferrous sulfate solution for a period of time, centrifuging, washing the obtained solid with deionized water, and drying; s2, oxidation reaction: adding the prepared peroxyacetic acid solution into sulfamethoxazole wastewater, adjusting the initial pH of the wastewater, adding a proper amount of catalyst, and carrying out oxidation reaction at normal temperature and normal pressure under the stirring condition. The catalytic material adopted by the invention is simple to prepare, easy to store, high in activation efficiency and low in dissolution rate of active components; the activated peracetic acid system has strong oxidizability, the treatment process has a sterilization function, the combination of advanced treatment and disinfection treatment functions of wastewater is realized, the activated peracetic acid system has strong process compatibility with modern sewage treatment plants, the sulfamethoxazole has high degradation efficiency, mild reaction conditions and low cost, and is suitable for industrial large-scale wastewater treatment.

Description

Method for removing sulfonamides in water by activating peracetic acid with modified zeolite
Technical Field
The invention relates to an advanced oxidation method based on activated peroxyacetic acid, in particular to a method for utilizing Fe2+Method for removing sulfonamide antibiotics in water by using artificial zeolite activated peroxyacetic acid.
Background
The sulfonamide antibiotics are mainly applied to the fields of medical treatment, cultivation and the like, have strong migration capacity in the environment and are one of the main antibiotic pollutants in the water environment. At present, the sulfonamide antibiotics in surface water of China reach the ng/L level. In particular to sulfamethoxazole, the content of which in a part of water is even more than hundreds ng/L. In the inlet water of sewage treatment plants, the concentration of the sulfonamide antibiotics is higher. Because the existence of such pollutants in water seriously threatens the survival of aquatic animals and plants and the health of human bodies, the research and development of efficient and environment-friendly technology is necessary to effectively treat the pollutants.
At present, methods for removing sulfonamide antibiotics in water bodies include: coagulation flotation, activated carbon adsorption, activated sludge, biofilm, advanced oxidation, and the like. There are three broad categories of biological, physicochemical and chemical treatment techniques. However, the selectivity of the physicochemical treatment technology is poor, the treatment process is only a simple process of transferring and concentrating pollutants, and secondary pollution exists; although the literature reports that biodegradation is also a way for removing sulfonamides antibiotics, the strain culture process is long, the strain can be inhibited by other fungi in application, and the requirement of industrial application is difficult to achieve at present. Compared with the method, the advanced oxidation technology has the characteristics of wide application range, high treatment efficiency and the like, and the treatment process changes the chemical structure of pollutants, so that the pollutants are converted into harmless inorganic substances or micromolecular organic substances which are easy to biodegrade, and the method has remarkable advantages.
However, the advanced oxidation also has problems of high treatment cost or difficulty in industrialization. Particularly aiming at novel PPCPs pollutants such as sulfonamide antibiotics, a conventional sewage treatment plant is difficult to be fused with a targeted purification process in the existing treatment process. Therefore, the selection of an advanced oxidation technology which has low application cost, small secondary pollution and strong compatibility with the water purification process of a modern sewage treatment plant is one of the key breakthrough openings for removing the sulfonamide antibiotics in water at present. The mainstream oxidant used in advanced oxidation technology to date is hydrogen peroxide, which generates hydroxyl radicals to rapidly mineralize organic pollutants and convert the organic pollutants into H2O and O2The secondary pollution is very small. However, the conditions for transporting and storing hydrogen peroxide are harsh, the reaction process is easily affected by the ambient temperature and the reaction pH, and strong oxidation property is usually exhibited in an acidic atmosphere, which increases the operation cost and the management difficulty. In recent years, peracetic acid (PAA) has been widely used in water treatment as a high-efficiency bactericide with high killing efficiency, no toxic disinfection by-products, and a wide suitable temperature range, and has a tendency to gradually replace the traditional chlorine disinfection, but the research on the application of PAA in advanced oxidation treatment of sewage is rarely reported. Peroxyacetic acid has a structure similar to that of hydrogen peroxide, contains O-O bonds, and has CH in comparison with H in hydrogen peroxide3The COO-group has a stronger electron-withdrawing ability, so that the O-O bond in peracetic acid is slightly stronger than that in hydrogen peroxidethe-O bond has high stability, and the low-concentration solution is easy to store. If the proper technology is adopted to enhance the oxidation capacity of the peroxyacetic acid system, and the strong disinfection function is combined, the technology can be well coupled with the process of the modern sewage treatment plant, and the method has a good development prospect.
Cleavage of the O-O bond of the peroxyacetic acid to CH by suitable activation3COO·、CH3CO3Radicals such as HO and HO can greatly enhance the oxidation capability of the system. Currently, commonly used activation methods include thermal activation, photoactivation, transition metal activation, and the like. In contrast to energy activation, Fe2+The activation technology has low application cost and high activation efficiency, and is easier for industrial application. However, Fe2+Is easily oxidized by dissolved oxygen and the like to lose efficacy, Fe2+Low utilization efficiency and is therefore based on Fe2+The homogeneous activation techniques of (a) generally require an acidic atmosphere. Further, Fe2+Solutions are difficult to store and generally require temporary preparation prior to use. In contrast, in the heterogeneous catalyst, the iron source is stably present in the internal structure of the material, the limitation degree by pH and the like is low, hydroxide precipitation is rarely generated in the reaction, the metal dissolution rate is low, the material reusability is good, and the practicability is stronger. The core of the heterogeneous activation technology is the preparation of efficient and cheap catalysts.
The artificial zeolite is a nonmetallic mineral with wide sources and large resource reserves, and has loose and porous large specific surface area, so that the artificial zeolite is increasingly widely applied to the field of materialization. The heterogeneous activating catalyst of the peroxyacetic acid system is prepared by utilizing the characteristics of easy preparation, easy modification and regeneration of the artificial zeolite, and is an effective mode. By using Fe as a support2+Artificial zeolite (Fe)2+Artificial zeolite) activated peracetic acid to treat sulfonamide antibiotic wastewater, greatly improves economic and environmental benefits, and reduces social environmental protection pressure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for utilizing Fe2+The method for removing sulfonamide antibiotics in water by activating peroxyacetic acid with artificial zeolite aims to achieve the effects of simple treatment process, mild conditions and easy industrial scale implementation.
The purpose of the invention is realized by the following technical scheme: a method for removing sulfonamides in water by activating peracetic acid with modified zeolite utilizes Fe with wide source, low cost, simple preparation method and high activity2+The artificial zeolite catalyst is used for generating active species with strong oxidizing property by utilizing heterogeneous activation reaction of the artificial zeolite catalyst and peroxyacetic acid under mild conditions, and further degrading the selected representative sulfonamide antibiotic-sulfamethoxazole, and the method comprises the following steps:
s1, catalyst preparation: grinding artificial zeolite into uniform fine powder, weighing a certain mass, adding the fine powder into dilute sulfuric acid, stirring uniformly, standing for a period of time, washing with deionized water until the pH value is near neutral (6.8-7.2), and heating in a muffle furnace to 100 ℃ for drying. Adding a certain amount of dried fine powder into a ferrous sulfate solution, soaking for a period of time, washing for 3-4 times by using deionized water, centrifugally separating, and drying the solid to obtain Fe2+Artificial zeolite catalyst;
s2, oxidation reaction: adding the prepared peroxyacetic acid solution into the wastewater containing sulfamethoxazole, adjusting the initial pH of the wastewater by using sulfuric acid and sodium hydroxide solution, and adding a proper amount of Fe2+The artificial zeolite catalyst is used for oxidation reaction under the conditions of proper temperature and uniform stirring.
Further, grinding the artificial zeolite in the step S1 to 200-300 meshes, wherein the concentration of sulfuric acid adopted in acid washing is 0.05-0.1 mol/L, and the acid washing time is 19-24 h;
further, when the ferrous sulfate solution is prepared in step S1, the pH of the deionized water is adjusted to 2.0 to 3.0 with sulfuric acid, and ferrous sulfate heptahydrate is added to prepare Fe2+A solution with a molar concentration of 0.2-0.4 mol/L;
further, in the preparation of the catalyst described in step S1, the artificial zeolite is mixed with Fe2+The mass ratio is 55: 1-65: 1, and the loading time is 20-24 h;
further, the drying temperature of the catalyst in the step S1 is 70-100 ℃;
further, the concentration of the prepared peroxyacetic acid in the step S2 is 10-12 g/L;
further, the concentration of the peroxyacetic acid in the reaction solution in the step S2 is 50 mg/L-100 mg/L;
further, the amount of the catalyst added into the reaction solution in the step S2 is 1.0-2.0 g/L;
further, the concentration of sulfamethoxazole in the wastewater obtained in the step S2 is 0.1 mg/L-3.0 mg/L;
further, the optimal initial reaction pH value of step S2 is 6.0-8.0, the initial reaction pH value is 2.0-9.0, the reaction temperature is 25-35 ℃, the stirring speed is 400-500 rpm, and the reaction time is 20-30 min.
The principle of the invention is as follows: the artificial zeolite is a tetrahedron composed of three elements of Si, Al and O, and because the silicon-oxygen tetrahedron and the aluminum-oxygen tetrahedron can construct an infinitely-extended three-dimensional space frame, the zeolite has strong adsorption and ion exchange capacities and can efficiently trap Fe in a liquid phase2+Form Fe2+Artificial zeolite composite material. Using Fe2+Bound state and Fe liberated during the activation of peracetic acid by artificial zeolites2+All participate in the activation process of peroxyacetic acid, so that the peroxyacetic acid is quickly converted into free radicals with stronger activity, such as HO & the like. Wherein, Fe in a bound state2+Active species (mainly HO & free radical) generated by activating peracetic acid are generated in situ on the surface of the material and react with sulfamethoxazole, and free Fe2+The active species generated by activation are dispersed in the liquid phase, homogeneously oxidizing the contaminants. Due to Fe2+The artificial zeolite has large specific surface area and high probability of contacting with sulfamethoxazole molecules, so that heterogeneous oxidation reaction plays an important role in the pollutant degradation process. This conclusion was also confirmed by a homogeneous control experiment (see example 5, table 1 for details).
Further, Fe2+The artificial zeolite can adsorb a small part of sulfamethoxazole by the action of electrostatic bonding, van der waals force and the like, but an adsorption control experiment proves that the pollutant removal rate contributed by the action is only 5.6% (see the table 1 of the embodiment 5 for details). The reaction principle is shown in FIG. 1.
The invention has the following advantages:
1. the invention provides an efficient sulfanilamide antibiotic advanced oxidation removal technology based on a peracetic acid system, the pollutant removal efficiency is up to more than 99% in a short time under mild reaction conditions, the application cost is low, and the treatment process has the sterilization effect. The invention realizes the combination of advanced treatment and disinfection treatment functions of the wastewater, and has stronger compatibility with the process of the modern sewage treatment plant.
2. The invention adopts novel Fe2+Artificial zeolite as peroxyacetic acid activator for activating peroxyacetic acid on solid phase surface and in liquid phase to generate free radical with much higher activation efficiency than homogeneous Fe2+And (4) activating.
3. The invention adopts the artificial zeolite with wide source, low price and environmental protection as the catalyst carrier, the material has large specific surface and more pores, and can effectively load Fe through ion exchange action, van der Waals force and the like2+. Coating Fe with aluminum oxide in catalyst preparation process2+By the framework structure reducing Fe2+Contact with air increases material stability; after the reaction is finished, the solid-liquid separation performance is strong, the structure of the catalyst is not changed in the process, and hetero ions, Fe, are not introduced into the liquid phase2+The dissolution amount is low, and secondary pollution is avoided to a greater extent.
4. The whole treatment process has simple process and mild reaction conditions, can efficiently degrade the sulfonamide pollutants under the conditions of neutral pH, normal temperature and normal pressure, and is easy for industrial large-scale implementation.
5. The method is suitable for wide pH range, can be applied to the direct treatment of strong acid and alkaline wastewater, does not introduce additional acid and alkali addition cost, and has wide application range.
Drawings
FIG. 1 is a schematic diagram of the mechanism of the present invention.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1: by using Fe2+Method for removing sulfonamide antibiotics in water by activating peroxyacetic acid with artificial zeoliteThe method comprises the following steps:
s1, catalyst preparation: grinding artificial zeolite into 200-mesh uniform fine powder, weighing a certain mass, adding into dilute sulfuric acid with the concentration of 0.05mol/L to enable the acid solution to just immerse the powder, stirring uniformly and standing for 24 hours. Washing with deionized water until pH is 6.8, heating in a muffle furnace to 100 deg.C, and oven drying. According to zeolite, Fe2+Adding a certain amount of dried fine powder into a ferrous sulfate solution with the concentration of 0.2mol/L according to the mass ratio of 60:1, soaking for 20 hours, washing for 3-4 times by using deionized water, carrying out centrifugal separation, and drying the solid in an oven at 100 ℃ to obtain the catalyst.
S2, oxidation reaction: 0.4mL to 50mL of peroxyacetic acid solution with the concentration of 10g/L is added into sulfamethoxazole wastewater with the concentration of 0.1mg/L, sulfuric acid and sodium hydroxide solution are used for adjusting the initial pH of the wastewater to be 6.0, 0.05g of catalyst is added into the mixed solution, and the reaction is carried out for 30min under the conditions that the temperature is 25 ℃ and the stirring speed is 500 rpm.
The sulfamethoxazole concentration after the reaction is measured to be 0mg/L, the corresponding removal rate is 100 percent, and the iron dissolution rate is 0.07 percent.
(Note: sulfamethoxazole detection method: determination by high performance liquid chromatography (Waters2695, USA))
Example 2: by using Fe2+The process of eliminating sulfonamide antibiotics from water with artificial zeolite activated peroxy acetic acid includes the following steps:
s1, catalyst preparation: grinding artificial zeolite into 200-mesh uniform fine powder, weighing a certain mass, adding into dilute sulfuric acid with the concentration of 0.1mol/L to ensure that the acid solution just immerses the powder, stirring uniformly and standing for 19 hours. Washing with deionized water until pH is 7.0, heating in a muffle furnace to 100 deg.C, and oven drying. According to zeolite, Fe2+Adding a certain amount of dried fine powder into a ferrous sulfate solution with the concentration of 0.2mol/L according to the mass ratio of 55:1, soaking for 24 hours, washing for 3-4 times by using deionized water, carrying out centrifugal separation, and drying the solid in an oven at 70 ℃ to obtain the catalyst.
S2, oxidation reaction: 0.5mL to 100mL of 0.5mg/L sulfamethoxazole wastewater with peracetic acid solution of 10g/L is added, the initial pH of the wastewater is adjusted to 7.0 by sulfuric acid and sodium hydroxide solution, 0.15g of catalyst is added into the mixed solution, and the reaction is carried out for 20min at the temperature of 35 ℃ and the stirring speed of 450 rpm.
The sulfamethoxazole concentration after the reaction is measured to be 0mg/L, the corresponding removal rate is 100 percent, and the iron dissolution rate is 0.05 percent.
(Note: sulfamethoxazole detection method: determination by high performance liquid chromatography (Waters2695, USA))
Example 3: by using Fe2+The process of eliminating sulfonamide antibiotics from water with artificial zeolite activated peroxy acetic acid includes the following steps:
s1, catalyst preparation: grinding artificial zeolite into 300-mesh uniform fine powder, weighing a certain mass, adding into dilute sulfuric acid with the concentration of 0.1mol/L to enable the acid solution to just immerse the powder, stirring uniformly and standing for 24 hours. Washing with deionized water until pH is 6.8, heating in a muffle furnace to 100 deg.C, and oven drying. According to zeolite, Fe2+Adding a certain amount of dried fine powder into a ferrous sulfate solution with the concentration of 0.4mol/L according to the mass ratio of 65:1, soaking for 24 hours, washing for 3-4 times by using deionized water, carrying out centrifugal separation, and drying the solid in an oven at 90 ℃ to obtain the catalyst.
S2, oxidation reaction: adding 2.0mL to 200mL of peroxyacetic acid solution with the concentration of 10g/L into 1.5mg/L sulfamethoxazole wastewater, adjusting the initial pH of the wastewater to 8.0 by using sulfuric acid and sodium hydroxide solution, adding 0.4g of catalyst into the mixed solution, and reacting for 30min at the temperature of 30 ℃ and the stirring speed of 450 rpm.
After the reaction, the sulfamethoxazole concentration is 0mg/L, which corresponds to 100% removal rate and 0.05% dissolution of iron.
(Note: sulfamethoxazole detection method: determination by high performance liquid chromatography (Waters2695, USA))
Example 4: by using Fe2+The process of eliminating sulfonamide antibiotics from water with artificial zeolite activated peroxy acetic acid includes the following steps:
s1, catalyst preparation: grinding artificial zeolite into 200-mesh uniform fine powder, weighing a certain mass, adding into dilute sulfuric acid with the concentration of 0.1mol/L to ensure that the acid solution just immerses the powder, stirring uniformly and standing for 20 hours. Is removed fromWashing with water until pH is 7.2, heating in a muffle furnace to 100 deg.C, and oven drying. According to zeolite, Fe2+Adding a certain amount of dried fine powder into a ferrous sulfate solution with the concentration of 0.3mol/L according to the mass ratio of 55:1, soaking for 20 hours, washing for 3-4 times by using deionized water, carrying out centrifugal separation, and drying the solid in an oven at 90 ℃ to obtain the catalyst.
S2, oxidation reaction: adding 1.5mL to 200mL of peroxyacetic acid solution with the concentration of 12g/L into 3.0mg/L sulfamethoxazole wastewater, adjusting the initial pH of the wastewater to 8.0 by using sulfuric acid and sodium hydroxide solution, adding 0.3g of catalyst into the mixed solution, and reacting for 25min at the temperature of 25 ℃ and the stirring speed of 450 rpm.
After the reaction, the sulfamethoxazole concentration is 0.03mg/L, the corresponding removal rate is 99.0 percent, and the iron dissolution rate is 0.03 percent.
(Note: sulfamethoxazole detection method: determination by high performance liquid chromatography (Waters2695, USA))
Example 5: single factor experimental study
(Note: 1. the method adopted in this case for the preparation of the catalyst is that the artificial zeolite is ground into 200 mesh even fine powder, a certain mass is weighed and added into dilute sulphuric acid with the concentration of 0.1mol/L, the acid solution is just immersed into the powder, the mixture is stirred evenly and kept stand for 20h, the mixture is washed by deionized water until the pH value is 7.2, the mixture is heated to 100 ℃ in a muffle furnace and dried, according to the weight of zeolite and Fe, the method is that2+Adding a certain amount of dried fine powder into a ferrous sulfate solution with the concentration of 0.2mol/L according to the mass ratio of 55:1, soaking for 20 hours, washing for 3-4 times by using deionized water, carrying out centrifugal separation, and drying the solid in an oven at 90 ℃ to obtain the catalyst. 2. The volume of the reaction liquid adopted by the sulfamethoxazole degradation reaction is 100 mL. 3. The sulfamethoxazole detection method comprises the following steps: the measurement was carried out by high performance liquid chromatography (Waters2695, USA). )
Oxidation system control test: a
The peroxyacetic acid alone oxidized the control test conditions: sulfamethoxazole concentration is 1.0mg/L, peracetic acid dosage is 100mg/L, reaction initial pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm.
The adsorption control test conditions were: sulfamethoxazole concentration is 1.0mg/L, catalyst dosage is 1.0g/L, initial reaction pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm.
The homogeneous control test conditions were: sulfamethoxazole concentration is 1.0mg/L, ferrous sulfate heptahydrate dosage is 80mg/L, peracetic acid dosage is 100mg/L, reaction initial pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm.
The heterogeneous test conditions were: sulfamethoxazole concentration is 1.0mg/L, catalyst dosage is 1.0g/L, peracetic acid dosage is 100mg/L, reaction initial pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm. The results are shown in Table 1.
TABLE 1 Sulfamethoxazole removal in different systems
Serial number Test group Sulfamethoxazole removal rate (%)
1 Peroxyacetic acid alone oxidation control test 29.9
2 Adsorption control test 5.6
3 Homogeneous phase control test 32.8
4 Heterogeneous assay 100.0
Degradation test at different initial pH conditions:
the test conditions were: sulfamethoxazole concentration is 1.0mg/L, catalyst dosage is 1.0g/L, peracetic acid dosage is 100mg/L, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm. The results are shown in Table 2.
TABLE 2 Sulfamethoxazole removal at different initial pH' s
Serial number Initial pH value Sulfamethoxazole removal rate (%)
1 2.0 98.6
2 3.0 99.4
3 4.0 99.3
4 5.0 99.8
5 6.0 100.0
6 7.0 100.0
7 8.0 100.0
8 9.0 99.7
Degradation tests under different reaction time conditions:
the test conditions were: sulfamethoxazole concentration was 1.0mg/L, catalyst addition was 1.0g/L, peracetic acid addition was 100mg/L, initial reaction pH was 7.0, reaction temperature was 25 ℃, and magnetic stirring speed was 450 rpm. The results are shown in Table 3.
TABLE 3 Sulfamethoxazole removal at different reaction times
Serial number Time (min) Sulfamethoxazole removal rate (%)
1 0 0
2 0.5 54.2
3 1 67.5
4 3 81.6
5 5 91.6
6 7 96.2
7 10 98.9
8 20 99.3
9 30 100.0
Degradation test of sulfamethoxazole at different concentrations:
the test conditions were: the adding amount of the catalyst is 1.0g/L, the adding amount of the peroxyacetic acid is 100mg/L, the initial pH of the reaction is 7.0, the reaction time is 30min, the reaction temperature is 25 ℃, and the magnetic stirring speed is 450 rpm. The results are shown in Table 4.
TABLE 4 removal of sulfamethoxazole at different concentrations
Serial number Sulfamethoxazole initial concentration (mg/L) Sulfamethoxazole removal rate (%)
1 0.1 99.0
2 0.3 100.0
3 0.5 100.0
4 1 100.0
5 2 100.0
6 3 99.6
7 4 96.3
8 5 95.5
Degradation tests under different catalyst addition conditions:
the test conditions were: sulfamethoxazole concentration is 1.0mg/L, peracetic acid dosage is 100mg/L, reaction initial pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm. The results are shown in Table 5.
TABLE 5 Sulfamethoxazole removal at different catalyst dosages
Serial number Catalyst dosage (g/L) Sulfamethoxazole removal rate (%)
1 0 29.9
2 0.1 75.5
3 0.2 89.2
4 0.5 92.0
5 1.0 97.3
6 1.5 98.3
7 2.0 100.0
Degradation tests at different amounts of peracetic acid added:
the test conditions were: sulfamethoxazole concentration is 1.0mg/L, catalyst dosage is 1.0g/L, initial reaction pH is 7.0, reaction time is 30min, reaction temperature is 25 ℃, and magnetic stirring speed is 450 rpm. The results are shown in Table 6.
TABLE 6 Sulfamethoxazole removal at different peracetic acid dosages
Figure GDA0001759216020000081

Claims (10)

1. A method for removing sulfonamides in water by activating peracetic acid with modified zeolite is characterized in that the screening adopts Fe which is wide in source, low in price, simple in preparation method and high in activity2+Artificial zeolite catalyst and method for degrading pollutants by using heterogeneous activation reaction of artificial zeolite catalyst and peroxyacetic acid under mild conditions to generate active species with strong oxidizing propertyThe method comprises the following steps:
s1. catalyst preparation: grinding artificial zeolite into fine powder, adding into dilute sulfuric acid, acid washing, stirring, standing for a period of time, washing with deionized water until pH is neutral, and heating to 100 in ovenoC, drying; adding a certain amount of dried fine powder into a ferrous sulfate solution, soaking for a period of time, washing for 3-4 times by using deionized water, centrifugally separating, and drying the solid to obtain Fe2+Artificial zeolite catalyst;
s2, oxidation reaction: adding the prepared peroxyacetic acid solution into the sulfonamide antibiotic wastewater, adjusting the initial pH of the wastewater to be in a proper range by using sulfuric acid and sodium hydroxide solution, and adding a proper amount of Fe2+The artificial zeolite catalyst is used for oxidation reaction under the conditions of proper temperature and uniform stirring.
2. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: grinding the artificial zeolite in the step S1 to fine powder of 200-300 meshes, wherein the concentration of sulfuric acid adopted for acid washing is 0.05-0.1 mol/L, and the acid washing time is 19-24 h.
3. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: when preparing the ferrous sulfate solution in the step S1, adjusting the pH of deionized water to 2.0-3.0 by using sulfuric acid, and adding ferrous sulfate heptahydrate to enable Fe2+The molar concentration is 0.2-0.4 mol/L.
4. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: in the preparation of the catalyst described in step S1, the artificial zeolite is mixed with Fe2+The mass ratio is 55: 1-65: 1, and the zeolite soaking time is 20-24 h.
5. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: the concentration of the prepared peroxyacetic acid in the step S2 is 10-12 g/L.
6. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: the concentration of the peroxyacetic acid in the reaction solution in the step S2 is 50 mg/L-100 mg/L.
7. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: fe described in step S22+The adding amount of the artificial zeolite catalyst is 1.0 g/L-2.0 g/L.
8. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: and S2, wherein the concentration of sulfamethoxazole is 0.1-3.0 mg/L.
9. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: the oxidation reaction of step S2 has an optimum initial reaction pH of 6.0-8.0 and a reaction temperature of 25-35oC, stirring speed is 400-500 rpm, and reaction time is 20-30 min.
10. The method for removing sulfonamides in water by using the peroxyacetic acid activated by the modified zeolite as claimed in claim 1, wherein the method comprises the following steps: the oxidation reaction of step S2 is suitably carried out at an initial reaction pH of 2.0 to 9.0 and a reaction temperature of 25 to 35oC, stirring speed is 400-500 rpm, and reaction time is 20-30 min.
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