CN113044949B - Sodium persulfate slow release agent suitable for catalytic oxidation degradation of antibiotics and preparation and application thereof - Google Patents
Sodium persulfate slow release agent suitable for catalytic oxidation degradation of antibiotics and preparation and application thereof Download PDFInfo
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- CN113044949B CN113044949B CN202110259970.3A CN202110259970A CN113044949B CN 113044949 B CN113044949 B CN 113044949B CN 202110259970 A CN202110259970 A CN 202110259970A CN 113044949 B CN113044949 B CN 113044949B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention discloses a sodium persulfate slow-release agent suitable for catalytic oxidation degradation of antibiotics, a preparation method thereof and application thereof in remediation of soil and underground water polluted by antibiotics. The sodium persulfate slow-release agent comprises the following raw materials by taking the total mass of the raw materials as 100 percent: 30-50% of paraffin, 30-50% of quartz sand, 1-4% of ordered mesoporous manganese oxide and 10-20% of sodium persulfate; the ordered mesoporous manganese oxide is prepared by a hard template method, and the template agent adopts SBA-15. The preparation method comprises the following steps: (1) adding paraffin into absolute ethyl alcohol, heating to 60-80 ℃, and after the paraffin is completely melted, sequentially adding a surfactant, quartz sand, ordered mesoporous manganese oxide and sodium persulfate into the paraffin under stirring; (2) and (3) cooling the molten material obtained in the step (1) to obtain the sodium persulfate slow release agent. The sodium persulfate slow release agent has the advantages of good coating effect, low release rate, good permeability and adsorptivity and good oxidative degradation characteristic.
Description
Technical Field
The invention relates to the technical field of soil and underground water remediation, in particular to sodium persulfate (Na) suitable for catalytic oxidative degradation of antibiotics2S2O8) Sustained release agent and its preparation and application.
Background
With the continuous development of economic society, the soil and underground water environment in China is seriously threatened by pollution in recent years. In particular, groundwater is extremely troublesome in treating pollutants in groundwater because of its complex geological properties, soil encapsulation, groundwater kinetics and microbial synergy, which allow the concealment of pollutants therein. If only natural degradation is relied on, the organic pollutants can reach the harmless level for hundreds to thousands of years, so that a practical and effective treatment mode needs to be developed to solve the pollution of soil and underground water.
In recent years, more and more antibiotics are discharged into soil and groundwater, and attention of broad students is paid to how to solve the problem of antibiotic pollution. Due to the tough characteristics and complex migration characteristics of antibiotic pollutants represented by tetracycline, researchers often have no way to the antibiotic pollutants, soil can become a shelter for the pollutants, and the repairing agent cannot intensively treat the pollutants; moreover, tetracycline can release pollution to underground water continuously by utilizing the characteristics of soil coating effect and the like, so that the continuous pollution effect is caused. Therefore, the problem cannot be solved well by a simple treatment mode, and the solution of the problem becomes the target of a plurality of researchers.
The chemical oxidation type slow release agent is generated under the condition, and the slow release agent can be used for carrying out accurate targeted treatment on pollutants in a common repair mode, has longer sustained release time, can effectively treat the pollutants reversely released from a low-permeability aquifer, and can also control the release speed of reactant amount. The chemical oxidation type slow release agent is expected to treat tetracycline in soil and underground water.
Yang yuan et al have studied the release property of sodium persulfate-paraffin-silica sand slow release material and its degradation effect on 2, 4-dinitrotoluene, and are expected to be used for in-situ chemical oxidation remediation of soil and groundwater (release property of sodium persulfate slow release material and its degradation effect on 2, 4-dinitrotoluene, environmental science research, 3 months 2020, No. 33, No. 3).
The Zhang Lina Master's academic paper research on the degradation of organic pollutants in groundwater by activating sodium persulfate with ferroferric oxide reports the effect of activating sodium persulfate to degrade 1, 2-dichloropropane by using transition metal oxides such as manganese dioxide as an activator, but the manganese dioxide is not deeply studied.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a sodium persulfate slow-release agent suitable for catalytic oxidative degradation of antibiotics, wherein sodium persulfate is used as a main oxidant, ordered mesoporous manganese oxide is used as a catalyst, and the sodium persulfate slow-release agent and the ordered mesoporous manganese oxide can be used for efficiently catalyzing oxidative degradation of antibiotics such as tetracycline and the like in cooperation. In addition, the invention takes paraffin as a carrier, and simultaneously adds quartz sand to enhance permeability and adsorptivity. The sodium persulfate slow-release agent has the advantages of good coating effect, low release rate, good permeability and adsorptivity and good oxidative degradation characteristic, and is particularly suitable for repairing soil and underground water polluted by antibiotic pollutants.
A sodium persulfate slow-release agent suitable for catalytic oxidation degradation of antibiotics comprises the following raw materials by taking the total mass of the raw materials as 100 percent:
the ordered mesoporous manganese oxide is prepared by a hard template method, and the template agent adopts SBA-15.
Research shows that when the common commercial manganese dioxide is used as a catalyst and is used together with sodium persulfate for treating antibiotics such as tetracycline, a good catalytic oxidation effect cannot be generated. When the ordered mesoporous manganese oxide prepared by using SBA-15 as a template and a hard template method is used as a catalyst and is used for treating antibiotics such as tetracycline and the like together with sodium persulfate, the synergistic effect of the catalyst and the sodium persulfate shows that the performance of catalyzing, oxidizing and degrading the antibiotics such as tetracycline and the like is obviously better, which shows that the ordered mesoporous manganese oxide has excellent catalytic action on the sodium persulfate and can furthest exert the oxidation performance of the sodium persulfate.
In order to better realize the catalytic function, the ordered mesoporous manganese oxide is preferably beta-MnO2Crystal structure of Mn-containing4+And Mn3+Specific surface area of not less than 80m2(ii) in terms of/g. With Mn at the same time4+、Mn3+The two valence state ordered mesoporous manganese oxides which can be mutually converted have better catalytic performance and electron transfer and transfer capability.
The hard template method preferably adopts a method for preparing a manganese oxide mesoporous material by a nano etching method which is published by Yankexin et al in 8 months of 2020 at volume 40, No. 8 of environmental science and is described in a method for preparing a manganese oxide ordered mesoporous material by degrading rhodamine B in high-salt-content wastewater.
Specifically, the hard template method preferably includes the steps of:
(I) adding a manganese nitrate aqueous solution into an absolute ethyl alcohol suspension of SBA-15, stirring for full adsorption, adding ammonia water to adjust the pH value of a reaction system to 10.5-11.5, continuously stirring for 10-20 min, then carrying out centrifugal separation, washing a solid product until the solid product is neutral, drying at normal temperature, and calcining at 350-450 ℃ for 3-5 h to obtain a calcined product;
(II) replacing SBA-15 with the calcined product, repeating the step (I), and carrying out 1-3 iterations in total to obtain a composite product;
(III) uniformly dispersing the composite product in a sodium hydroxide solution, heating and boiling, reacting under a reflux condition to remove SBA-15, centrifugally separating after the reaction is finished, washing solid precipitate until the solid precipitate is neutral, and drying in vacuum at 55-65 ℃ to obtain the ordered mesoporous manganese oxide.
The ordered mesoporous manganese oxide prepared by the hard template method has high order degree and crystallinity, good adsorption and catalytic capacity, extremely strong catalytic capacity especially for the process of sodium persulfate, tetracycline oxide and other antibiotics, and strong recycling stability.
Preferably, the mass ratio of the sodium persulfate to the ordered mesoporous manganese oxide is 5-10: 1, and more preferably 5-8: 1. The addition amount of the ordered mesoporous manganese oxide is in positive correlation with the catalytic capability, but when the addition amount of the catalyst exceeds a certain proportion, the addition amount of the catalyst is increased, and the promotion degree of the catalytic reaction promotion effect of the catalyst is weakened.
The sodium persulfate slow release agent adopts paraffin and quartz sand as a mixed carrier, wherein: the paraffin has good adhesiveness, is insoluble in water and is an environment-friendly material; the quartz sand has good permeability and is a green and environment-friendly material. The mixed carrier increases the coating effect, permeability and adsorbability of the sustained release agent.
The invention also provides a preparation method of the sodium persulfate slow-release agent, which comprises the following steps:
(1) adding paraffin into absolute ethyl alcohol, heating to 60-80 ℃, and after the paraffin is completely melted, sequentially adding a surfactant, quartz sand, ordered mesoporous manganese oxide and sodium persulfate into the paraffin under stirring;
(2) and (3) cooling the molten material obtained in the step (1) to obtain the sodium persulfate slow release agent.
The melting temperature range of the paraffin is 58-60 ℃, so in the step (1), the temperature of the system is controlled to be 60-80 ℃ when the paraffin is dissolved, and the paraffin can be completely melted. Preferably, the heating in the step (1) is carried out to 70-75 ℃, so that the transfer of the molten material in the step (2) is facilitated, and the subsequent cooling is facilitated.
In the step (1), the surfactant comprises span-80 and polyethylene glycol with the molecular weight of 4000, and plays a role in emulsification. The mass ratio of span-80 to polyethylene glycol is preferably 0.01-0.2: 1. The mass ratio of the absolute ethyl alcohol to the polyethylene glycol is preferably 1-20: 1. Polyethylene glycol can also act as a dissolution aid to aid in paraffin dissolution.
Preferably, in the step (1), the rotation speed of the stirring is 100-200 rpm, and the total stirring time is 5-30 min.
The melted slow release agent is in a flowing state before molding, and once the paraffin is cooled, the paraffin is quickly condensed, so that the molding time is short. In the step (2), in order to enable the sodium persulfate slow-release agent obtained by cooling to have a fixed shape and size, the molten material obtained in the step (1) can be poured into a mold for cooling to obtain the sodium persulfate slow-release agent.
The specific dimensions of the mould may be 1.0cm x 1.0 cm.
The principle of the preparation method is as follows: based on a controlled release technology and a microcapsule technology, an oxidant sodium persulfate and a catalyst ordered mesoporous manganese oxide are uniformly dispersed in a molten liquid taking paraffin, quartz sand and the like as carriers by using a melting condensation dispersion method, a reagent auxiliary carrier such as absolute ethyl alcohol, polyethylene glycol, span-80 and the like, the oxidant and the catalyst are added and uniformly and stably mixed, and finally the mixture is poured into a mold while the mixture is hot, cooled and dried to form solid particles so as to achieve the purpose of slow release.
The invention also provides application of the sodium persulfate slow-release agent in repairing soil and underground water polluted by antibiotics.
Preferably, the antibiotic is Tetracycline (TC). Research finds that antibiotics such as tetracycline and the like are very stable, single sodium persulfate cannot directly oxidize the antibiotics, and effective oxidative degradation of the antibiotics such as tetracycline and the like can be realized by the aid of the catalytic action of a specific catalyst.
Compared with the prior art, the invention has the main advantages that:
1) the sodium persulfate slow release agent disclosed by the invention takes sodium persulfate as a main oxidant, ordered mesoporous manganese oxide as a catalyst, paraffin as a carrier, and quartz sand is added to enhance the permeability and the adsorbability. The ordered mesoporous manganese oxide has the advantages of large specific surface area, high order degree and crystallinity, good recycling performance and unique excellent capability of catalyzing antibiotics such as sodium persulfate, tetracycline oxide and the like; the sodium persulfate slow-release agent has good coating effect, low release rate and good permeability and adsorbability, and can be used for repairing soil and underground water polluted by antibiotic pollutants such as tetracycline, and the oxidative degradation performance is remarkably improved under the synergistic catalytic action of the ordered mesoporous manganese oxide.
2) The preparation method of the sodium persulfate slow-release agent is based on a controlled release technology and a microcapsule technology, and comprises the steps of uniformly dispersing an oxidant sodium persulfate and a catalyst ordered mesoporous manganese oxide in molten liquid using paraffin, quartz sand and the like as carriers by using a melting condensation dispersion method, adding a reagent auxiliary carrier such as absolute ethyl alcohol, polyethylene glycol, span-80 and the like and the oxidant, uniformly and stably mixing, pouring the mixture into a mold while the mixture is hot, and cooling and drying the mixture to form solid particles so as to achieve the purpose of slow release.
3) The sodium persulfate slow-release agent has the advantages of obviously reduced release rate in water, enhanced permeability, enhanced adsorptivity and oxidability; meanwhile, the release period is prolonged, the release speed of the sustained-release agent is stable, and the method has a good treatment effect on TC-polluted soil and wastewater.
Drawings
FIG. 1 is a photograph of a real object of the sustained-release agent of example 3;
FIG. 2 is a graph of the static release sodium persulfate concentration versus time for the sustained release formulation of example 3;
FIG. 3 is a graph of the relative concentration of tetracycline over time in a slow release static remediation experiment of example 3;
FIG. 4 is a graph of sodium persulfate concentration versus time for the dynamic release experiment of example 3, where the CRM tag represents the sustained release agent of example 3;
FIG. 5 is a graph of the relative concentration of tetracycline over time in the dynamic repair experiment of example 3, where the CRM tag represents the extended release formulation of example 3;
FIG. 6 is a graph of the relative concentration change of different catalysts of test example 1 on tetracycline degradation;
FIG. 7 is a graph showing the change of tetracycline relative concentration for six hours of static remediation by sustained release agents with different amounts of ordered mesoporous manganese oxide in test example 2;
FIG. 8 is a graph showing the variation in sodium persulfate concentration for six hours of static release for controlled release formulations of varying wax to sand ratios for test example 3;
FIG. 9 is a graph showing the change in the concentration of sodium persulfate at six hours of static release for various amounts of sodium persulfate added in test example 4.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The preparation method of the ordered mesoporous manganese oxide in the specific embodiment comprises the following steps:
(I) adding 4mL of a 50 wt% manganese nitrate aqueous solution into 50mL of an absolute ethyl alcohol suspension containing 3g of SBA-15, stirring at 0 ℃ for 4h for full adsorption, adding ammonia water to adjust the pH value of a reaction system to 11, continuously stirring for 15min, performing centrifugal separation, washing a solid product until the solid product is neutral, drying at normal temperature, and calcining at 400 ℃ for 4h to obtain a calcined product;
(II) replacing SBA-15 with the calcined product, and repeating the step (I) to obtain a composite product;
(III) uniformly dispersing the composite product in 200mL of 2mol/L sodium hydroxide solution, heating and boiling, reacting under a reflux condition to remove SBA-15, centrifugally separating after the reaction is finished, washing solid precipitate until the solid precipitate is neutral, and vacuum drying at 60 ℃ for 24 hours to obtain the ordered mesoporous manganese oxide.
Example 1
Commercial manganese dioxide (national chemical group chemical reagent Co., Ltd., analytical pure) is used as a catalyst to catalyze sodium persulfate to degrade tetracycline, the initial concentration of the tetracycline is controlled to be 20mg/L, the catalyst is 0.1g/L, and Na2S2O8＝2mmol/L。
Example 2
The ordered mesoporous manganese oxide is used as a catalyst to catalyze sodium persulfate to degrade tetracycline, the initial concentration of the tetracycline is controlled to be 20mg/L under the same test conditions as in example 1, the catalyst is 0.1g/L, and Na is added2S2O8＝2mmol/L。
Example 3
The slow release agent is a mixed adsorption slow release agent with the mass ratio of sodium persulfate to paraffin, quartz sand and mesoporous manganese dioxide being 4:12:12: 0.5.
(1) Preparation of sustained release agent
Based on microcapsule technology, adopts melting condensation dispersion method to prepare the slow release agent. Taking 12g of paraffin into a conical flask, adding 20mL of absolute ethyl alcohol, and heating to 75 ℃ in a water bath; after the paraffin is completely melted, adding 1g of polyethylene glycol-4000 and 2 drops of span-80, and fully stirring; adding 12g of quartz sand, 0.5g of ordered mesoporous manganese oxide and 4g of sodium persulfate powder in sequence according to the mass ratio of 4:12:12:0.5, and stirring to uniformly disperse the materials; pouring the hot mixture into a prepared mould with the specification of 1.0cm multiplied by 1.0 cm; cooling and drying to obtain the cube type solid novel sodium persulfate sustained-release agent.
FIG. 1 is a photograph showing the slow release agent prepared from sodium persulfate, paraffin, quartz sand and mesoporous manganese dioxide at a mass ratio of 4:12:12: 0.5.
(2) Sustained release formulation static release
The principle of the static release experiment is that different sustained-release agents are in the same liquid environment (water environment or organic solution environment), so that the oxidant sodium persulfate in the sustained-release agents is released but does not react. Sampling was carried out at set time points over a fixed period of time, and the sodium persulfate concentration was measured at various times using an ultraviolet spectrophotometer.
Placing about 2.0g of solid sustained-release agent in a 250mL conical flask; adding 250mL of water, and starting timing; respectively measuring 1mL of sample, 1mL of KI solution and 1mL of NaHCO in fixed time and quantity3Placing the solution in a 10mL colorimetric tube, fixing the volume to 10mL, recording the label (adding blank sample), and shaking up for 15min by hand; measuring absorbance of the sodium persulfate at 352nm using a spectrophotometer; the concentration is calculated, and a line graph is drawn. The time-dependent change in the concentration of sodium persulfate statically released from the sustained release formulation is shown in FIG. 2.
(3) Sustained release agent static remediation
Static repair experiments were simulated and a representative antibiotic contaminant, tetracycline, was selected. In the experiment, sodium persulfate is selected to treat tetracycline micro-polluted simulated underground water, and timing sampling measurement is carried out. The treatment effect of the sodium persulfate and tetracycline oxide catalyzed by the ordered mesoporous manganese oxide is good.
Preparing low-concentration tetracycline serving as polluted water; placing 2g of sustained release agent to be measured in a reactor, adding 100mL of polluted water, wherein the tetracycline content is 10 mg/L; sampling at regular intervals, and taking 5mL of the sample each time; the tetracycline concentration in the sample was measured by UV spectrophotometry at 352nm and plotted as a function of time, the results are shown in FIG. 3.
(4) Dynamic release and repair
The dynamic experiment mainly simulates the medium environment and the flow rate of underground water to carry out a one-dimensional sand column experiment. In this case, the contaminated groundwater was repaired with the mixed adsorption sustained release agent, and the repairing effect was observed. The experiment was performed in a one-dimensional sand column. The slow release agent is a mixed adsorption slow release agent with the mass ratio of sodium persulfate to paraffin, quartz sand and mesoporous manganese dioxide being 4:12:12: 0.5.
And simulating the medium environment and the flow rate of underground water to perform a one-dimensional sand column experiment. The experimental parameters simulate the groundwater environment setting. The permeability coefficient of the experimental column medium is 1.39 multiplied by 10-2cm/s; the water flow speed is set to be 2 mL/min; the diameter of the experimental column is R ═ 5.0 cm; the length of the experimental column is L ═ 20cm, wherein the specific length of the sustained-release agent is L13.0cm, front buffer medium ratio l21.0cm, ratio of actual medium l315.0cm, rear buffer medium ratio l4＝1.0cm。
Filling a one-dimensional sand column, and enabling water (or polluted water) in the one-dimensional sand column to be saturated (200 mL); 2g of sodium persulfate slow release agent is put at a water inlet of the one-dimensional sand column; connecting the one-dimensional sand column, the water tank and the peristaltic pump; starting a peristaltic pump; pumping water at a flow rate of 2.0 mL/min; starting a peristaltic pump, then sampling periodically, and measuring the sodium persulfate concentration (or tetracycline concentration) of each water sample; the sodium persulfate concentration (or tetracycline concentration) was plotted.
Dynamic release experiments: and (3) saturating the water in the experimental column filled with the medium, and adding 2g of slow release agent or sodium persulfate powder with the mass equivalent to that of the sodium persulfate in the 2g of slow release agent at the water inlet of the one-dimensional sand column. The water in the system was made a sodium persulfate solution, and the change in concentration with time was measured. The sodium persulfate concentration in the dynamic release experiment as a function of time is shown in FIG. 4.
Dynamic repair experiment: the experimental column medium was filled with tetracycline-contaminated water at an initial concentration of 10 mg/L. 2g of slow release agent or sodium persulfate powder which is equivalent to the mass of sodium persulfate in 2g of slow release agent is added at the water inlet of the experimental column. And connecting the peristaltic pump with the experimental column, and starting the peristaltic pump to perform a dynamic repair experiment. The tetracycline concentration in the dynamic repair experiments as a function of time is shown in figure 5.
Example 4
The preparation method of the sustained release agent is different from that of the example 3 only in that the addition amount of the ordered mesoporous manganese oxide is 0.3g, and the rest steps and conditions are the same.
Example 5
The preparation method of the sustained release agent is different from that of the example 3 only in that the addition amount of the ordered mesoporous manganese oxide is 0.7g, and the rest steps and conditions are the same.
Example 6
The preparation method of the slow release agent is different from that of the example 3 only in that the ordered mesoporous manganese oxide is not added, the dosage of the paraffin is 3g, and the other steps and conditions are the same.
Example 7
The sustained-release agent was prepared by the same method as in example 6 except that the amount of paraffin was 6g, and the remaining steps and conditions were the same.
Example 8
The sustained-release agent was prepared by the same method as in example 6 except that the amount of paraffin was 12g, and the remaining steps and conditions were the same.
Example 9
The sustained-release agent was prepared by the same method as in example 8 except that sodium persulfate was used in an amount of 2g, and the remaining steps and conditions were the same.
Example 10
The sustained-release agent was prepared by the same method as that of example 9 except that sodium persulfate was used in an amount of 6g, and the remaining steps and conditions were the same.
Test example 1
The effect of the different catalysts of examples 1,2 on tetracycline degradation is shown in figure 6. Therefore, different catalytic materials have different catalytic activities on sodium persulfate, and the ordered mesoporous manganese oxide has obviously better catalytic activity. The commercial manganese dioxide does not have an ordered mesoporous structure, has a small specific surface area and weak catalytic performance, and the ordered mesoporous manganese oxide has good performance, so that sodium persulfate and tetracycline can be in full contact reaction while a large amount of tetracycline is adsorbed; and the existence of a large amount of Mn is observed in the ordered mesoporous manganese oxide material3+/Mn4+Therefore, the ordered mesoporous manganese oxide has good catalytic performance, and is selected as a catalytic material in the slow release agent.
Test example 2
In order to study the influence of the addition amount of the ordered mesoporous manganese oxide on the effect of the sustained-release agent, 4 sustained-release agents in total in examples 3-5 and 8 are selected for carrying out a static repair experiment. The change chart of the tetracycline statically repaired by the slow release agent with different ordered mesoporous manganese oxide ratios for six hours is shown in figure 7. Therefore, the blank control group without the ordered mesoporous manganese oxide has almost no degradation effect on tetracycline, and the sodium persulfate which is only added is almost free from oxidative degradation effect on the tetracycline due to the over-stability of the sodium persulfate, SO that the sodium persulfate is activated by adding the ordered mesoporous manganese oxide to generate SO4 -To oxidize tetracycline. And sodium persulfate can be effectively catalyzed and tetracycline can be degraded only by adding a trace amount of ordered mesoporous manganese oxide, the more the amount of the ordered mesoporous manganese oxide is, the stronger the degradation effect of the sustained-release agent on tetracycline is, but the economic benefit can be reduced along with the further increase of the amount of the ordered mesoporous manganese oxide, and the amount of the catalyst added is consistent with the amount of the oxidant in consideration of economy. Therefore, the addition ratio of mesoporous manganese dioxide needs to be controlled to obtain the best effect.
Test example 3
In order to study the influence of different wax-sand ratios on the effect of the sustained-release agent, 3 sustained-release agents of examples 6, 7 and 8 were selected for dynamic repair experiments. The graph of the change of the sodium persulfate in the static release of the sustained release agent with different wax-sand ratios for six hours is shown in figure 8. Therefore, the wax sand ratio has a great influence on the release performance of the sustained release agent, and the more the paraffin content in the sustained release agent is, the slower the release rate of the sustained release agent is. The reason is that the more the paraffin content is, the more compact and compact the sustained release agent is, the slower the release of the sodium persulfate is, the less the paraffin content is, the looser the sustained release agent is integrally, the infirm package is realized, and the sodium persulfate is easily released from the sustained release agent. When the wax-sand ratio is 1:1, the sustained-release agent shows good sustained-release performance.
Test example 4
In order to study the influence of different oxidant contents on the effect of the sustained release agent, the 3 sustained release agents of examples 8, 9 and 10 were selected to perform dynamic repair experiments, and the change chart of sodium persulfate when the sustained release agent with different oxidant contents is statically released for six hours is shown in fig. 9. It can be seen that the more sodium persulfate is added, the faster sodium persulfate is released. When the addition amount is 2g, sodium persulfate is hardly released, and the release efficiency is extremely low probably due to the tight package of paraffin; the release effect of the sustained release agent added with the sodium persulfate with the mass of 4g is not much different from that of 6 g. Within 1 hour, the release rate of the sustained release agent is changed from fast to slow and then slowly reaches the equilibrium, and within the next 5 hours, the release rate is relatively stable, thus showing the excellent sustained release characteristic of the sustained release agent. Therefore, the larger the loading capacity of the oxidant in the sustained release agent is, the faster the release rate of the sustained release agent is, which indicates that the release concentration of the sustained release agent can be adjusted by changing the content of sodium persulfate in the sustained release agent, and the optimal treatment effect can be achieved by making corresponding adjustments according to the concentrations of pollutants in different places.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. The sodium persulfate slow-release agent suitable for catalytic oxidation degradation of antibiotics is characterized by comprising the following raw materials by taking the total mass of the raw materials as 100 percent:
30 to 50 percent of paraffin,
30-50% of quartz sand,
1 to 4 percent of ordered mesoporous manganese oxide,
10% -20% of sodium persulfate;
the ordered mesoporous manganese oxide is prepared by a hard template method, and a template agent adopts SBA-15;
the ordered mesoporous manganese oxide is beta-MnO2Crystal structure of Mn-containing4+And Mn3+Specific surface area of not less than 80m2/g；
The mass ratio of the sodium persulfate to the ordered mesoporous manganese oxide is 5-10: 1;
the hard template method comprises the following steps:
(I) adding a manganese nitrate aqueous solution into an absolute ethyl alcohol suspension of SBA-15, stirring for full adsorption, adding ammonia water to adjust the pH value of a reaction system to 10.5-11.5, continuously stirring for 10-20 min, then carrying out centrifugal separation, washing a solid product until the solid product is neutral, drying at normal temperature, and calcining at 350-450 ℃ for 3-5 h to obtain a calcined product;
(II) replacing SBA-15 with the calcined product, repeating the step (I), and carrying out 1-3 iterations in total to obtain a composite product;
(III) uniformly dispersing the composite product in a sodium hydroxide solution, heating and boiling, reacting under a reflux condition to remove SBA-15, centrifugally separating after the reaction is finished, washing solid precipitate until the solid precipitate is neutral, and drying in vacuum at 55-65 ℃ to obtain the ordered mesoporous manganese oxide.
2. The process for producing a sodium persulfate sustained-release agent according to claim 1, which comprises the steps of:
(1) adding paraffin into absolute ethyl alcohol, heating to 60-80 ℃, and after the paraffin is completely melted, sequentially adding a surfactant, quartz sand, ordered mesoporous manganese oxide and sodium persulfate into the paraffin under stirring;
(2) and (3) cooling the molten material obtained in the step (1) to obtain the sodium persulfate slow release agent.
3. The method for preparing a sodium persulfate sustained-release agent according to claim 2, wherein in the step (1), the surfactant comprises span-80 and polyethylene glycol with the molecular weight of 4000, the mass ratio of span-80 to polyethylene glycol is 0.01-0.2: 1, and the mass ratio of anhydrous ethanol to polyethylene glycol is 1-20: 1.
4. The method for preparing a sodium persulfate slow-release agent as defined in claim 2, wherein in the step (1), the temperature is raised to 70 to 75 ℃.
5. The method for preparing a sodium persulfate slow-release agent according to claim 2, wherein in the step (1), the rotation speed of the stirring is 100 to 200rpm, and the total stirring time is 5 to 30 min.
6. The process for producing a sodium persulfate slow-release agent as described in claim 2, wherein in the step (2), the molten material obtained in the step (1) is poured into a mold and cooled to obtain the sodium persulfate slow-release agent.
7. The use of the sodium persulfate slow-release formulation according to claim 1 for remediating antibiotic-contaminated soil and groundwater.
8. The use of claim 7, wherein the antibiotic is tetracycline.
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