CN112047450A - Preparation method and application of composite oxidant - Google Patents

Preparation method and application of composite oxidant Download PDF

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CN112047450A
CN112047450A CN202010768384.7A CN202010768384A CN112047450A CN 112047450 A CN112047450 A CN 112047450A CN 202010768384 A CN202010768384 A CN 202010768384A CN 112047450 A CN112047450 A CN 112047450A
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composite
ldh
oxidant
peroxide
composite oxidant
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潘全
陈魏
何瑜
宋功武
佘小燕
万小蕙
周建刚
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Hubei Fiber Inspection Bureau
Hubei University
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Hubei University
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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
    • 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
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F7/00—Aeration of stretches of water
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
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Abstract

The invention provides a preparation method and application of a composite oxidant, wherein the preparation method comprises the following steps: dissolving hydroxide solid in water to obtain suspension, adding stabilizer, stirring, and adding H2O2Reacting the solution for 10-30min, adding the suspension of the polymetallic hydrotalcite Cu-Zn-Fe-LDH prepared by the coprecipitation method, stirring until the suspension is uniform, and then adding H2O2The solution reacts for 10-30min, solid-liquid separation is carried out after the reaction, and the obtained solid is dried to obtain the composite material of peroxide and Cu-Zn-Fe-LDH as the composite oxidant. The invention also providesThe application of the composite oxidant can be used as a Fenton-like reagent without adding H2O2The polybrominated diphenyl ethers can be efficiently and quickly degraded by being combined with an ultrasonic method.

Description

Preparation method and application of composite oxidant
Technical Field
The invention belongs to the technical field of organic matter degradation, and particularly relates to a preparation method and application of a composite oxidant.
Background
Polybrominated diphenyl ethers (PBDEs) have been widely used as brominated flame retardants in electronic products, textiles, and household building materials. The biological organic fertilizer has biological accumulation and persistence, is very stable in the environment, is difficult to degrade and generates harm to human health, and becomes a research hotspot in the current international environmental field. As a persistent environmental pollutant, PBDEs are further studied deeply, and the degradation research of PBDEs is continuously perfected and developed. At present, PBDEs degradation research is mainly divided into chemical reduction, photodegradation, catalytic degradation and microbial degradation.
Among the processes for treating polybrominated diphenyl ethers, reductive degradation is the most studied process at present. Wherein the TiO is2The photocatalytic reduction method is one of the most efficient methods, which can effectively remove the precursor pollutant BDE209, but the low-bromine intermediate product generated in the reaction process is difficult to further reduce and debrominate. For example, in TiO2In the/CH 3CN system, although nonabromodiphenyl ether and octabromodiphenyl ether can be rapidly degraded, after being irradiated for 24 hours, a plurality of hexabromodiphenyl ether and pentabromodiphenyl ether are accumulated, and the low-bromine intermediate products generated in the degradation process of BDE209 are more difficult to degrade and reduce. Of further concern is the higher toxicity and greater stability of low brominated PBDEs homologues, and therefore the large amount accumulated during the reductive degradation of PBDEsThe low brominated product brings great harm to the environment. Therefore, a method for realizing deep reductive debromination of polybrominated diphenyl ethers is urgent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of a composite oxidant2O2The method is combined with an ultrasonic method, and can efficiently, quickly and deeply degrade polybrominated diphenyl ethers.
In order to achieve the above objects, in a basic embodiment, the present invention provides a method for preparing a complex oxidant, comprising the steps of:
dissolving hydroxide solid in water to obtain suspension, adding stabilizer, stirring, and adding H2O2Reacting the solution for 10-30min, adding the suspension of the polymetallic hydrotalcite Cu-Zn-Fe-LDH prepared by the coprecipitation method, stirring until the suspension is uniform, and then adding H2O2The solution reacts for 10-30min, solid-liquid separation is carried out after the reaction, and the obtained solid is dried to obtain the composite material of peroxide and Cu-Zn-Fe-LDH as the composite oxidant.
In a preferred embodiment, the hydroxide solids are selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide. Accordingly, the peroxide in the composite material is one or more of sodium peroxide, potassium peroxide and calcium peroxide.
In a preferred embodiment of the process according to the invention, the molar ratio of Zn, Fe and Cu in the multimetallic hydrotalcite Cu-Zn-Fe-LDH is controlled to be 1-10:1-10:1-10, respectively. The hydrotalcite has the best catalytic performance under the condition of the proportion.
In a preferred embodiment, the co-precipitation method for preparing the polymetallic hydrotalcite Cu-Zn-Fe-LDH comprises the following steps: respectively contain Cu2+Salt, containing Zn2+Salts and Fe-containing compounds2+Dissolving salt in water, stirring vigorously, controlling the pH value of the solution to be 6-7, stirring for 1-8h in a water bath at 40-50 ℃, aging for 1-8h, removing supernatant, centrifuging the lower-layer precipitate, and washing to obtain Cu-Zn-Fe-LDH precipitate.
According to the process of the invention, in a preferred embodiment, KH is used2PO4As a stabilizer.
According to the process of the invention, in a preferred embodiment, 1 to 10g of the hydroxide solid are dissolved in water to form a suspension, and 0.1 to 1g of KH are added2PO4Stirring for 20-40min, adding 1-10mL of 30% H2O2Reacting the solution for 10-30min, adding 10-100mL Cu-Zn-Fe-LDH suspension, stirring for 1-10min until uniform, and adding H2O2Reacting the solution, filtering after reacting for 10-30min, taking the upper layer precipitate, drying overnight at the temperature of 110-140 ℃ to obtain the composite material of peroxide and Cu-Zn-Fe-LDH, namely the composite oxidant.
The invention also aims to provide application of the composite oxidant, and the composite oxidant is used for adsorption degradation of polybrominated diphenyl ethers under the assistance of ultrasonic means.
Another aspect of the present invention is to provide a method for degrading polybrominated diphenyl ethers, comprising the following steps: adding the composite oxidant into an organic solvent solution of polybrominated diphenyl ethers (PBDEs), adjusting the pH to 2-6 with acid liquor, and degrading under an ultrasonic state.
According to the application of the invention, in a preferred embodiment, the mass ratio of the polybrominated diphenyl ether to the oxidizing agent is 1:20-1: 200; the organic solvent is preferably tetrahydrofuran, the polybrominated diphenyl ether is preferably decabrominated diphenyl ether, and the acid solution is preferably sulfuric acid.
According to the application of the present invention, in a preferred embodiment, the ultrasonic power is preferably 100w-800w, and the ultrasonic time is preferably 30-120 minutes.
The special layered structure of Layered Double Hydroxide (LDH) has adsorption effect on PBDEs, and its two metal ions are uniformly distributed in the structureIf the metal ion is a transition metal ion with catalytic degradation activity, the LDH has higher catalytic activity and selectivity, and the interlayer anions have good exchangeability. The use of LDH containing Fe enables a Fenton-like reaction to take place so that the degradation is complete. In Fenton-like reactions, OH radicals are required, which can generally be derived from H2O2Is obtained directly, however, H2O2Is unstable and is easy to decompose, and finally the utilization rate is not high; and H2O2The environment is polluted to a certain extent. The compounding of solid peroxide can overcome H2O2Easily decomposed inefficiently, and CaO in general2The peroxide is stable and convenient to store; meanwhile, the oxygen can be slowly released in the water body, and the oxygen environment of the water body is improved.
The invention has the following beneficial effects: according to the technical scheme, the solid peroxide is used as an oxygen source to form a composite material with the multi-metal iron-containing hydrotalcite to obtain the composite oxidant, the composite oxidant can be used as a Fenton-like reagent, and H does not need to be added2O2The method is combined with an ultrasonic method, and can efficiently, quickly and deeply degrade polybrominated diphenyl ethers.
Drawings
FIG. 1a shows peroxide (CaO)2) XRD pattern of (a); FIG. 1b is an XRD pattern of a Cu-Zn-Fe-LDH and peroxide composite (composite oxidant);
FIG. 2a is an infrared spectrum of peroxide; FIG. 2b is an infrared spectrum of a Cu-Zn-Fe-LDH and peroxide composite (composite oxidant);
FIG. 3a is a TEM image of a peroxide; FIG. 3b is a TEM image of Cu-Zn-Fe-LDH and peroxide composite (composite oxidant);
fig. 4 is a schematic diagram showing the efficiency of degrading polybrominated diphenyl ethers by using the complex oxidant prepared in example 1.
Fig. 5 is a schematic diagram showing the efficiency of degrading polybrominated diphenyl ethers by using the complex oxidant prepared in this example 2.
Fig. 6 is a schematic diagram showing the efficiency of degrading polybrominated diphenyl ethers by using the complex oxidant prepared in this example 3.
Fig. 7 is a schematic diagram showing the efficiency of degrading polybrominated diphenyl ethers by using the complex oxidant prepared in this example 4.
Detailed Description
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict. It should be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the examples of the present invention are commercially available or can be prepared by an existing method. The preparation method is described in detail below.
Example 1
Preparing multi-metal hydrotalcite Cu-Zn-Fe-LDH by a coprecipitation method, and controlling the molar ratio of Zn to Fe to Cu to be 1:8:1 respectively. Dissolving sulfate of three metals in water, stirring vigorously, controlling the pH value of the solution to be 7, stirring for 3h in a water bath at 40 ℃, finally aging for 3h, removing a supernatant, centrifuging the lower-layer precipitate for 15min at 5000rpm, washing, and continuously repeating for 3 times to obtain the Cu-Zn-Fe-LDH precipitate.
The composite oxidant is further synthesized by the following steps: 2g of Ca (OH)2Dissolving the solid in 10mL water to obtain a suspension, and adding 0.3g KH2PO4As a stabilizer, after stirring for 30min, 2mL of 30% H was added2O2The solution is reacted for 15min, if a mixed sample is prepared, 15mL of Cu-Zn-Fe-LDH suspension is added at this time, the mixture is stirred for 3min until the mixture is stirred uniformly, and 2mL of H is added2O2The solution reacts for 15min, then is filtered, the upper layer sediment is taken out and dried overnight at the temperature of 120 ℃, and CaO is obtained2And Cu-Zn-Fe-LDH as a composite oxidant. FIG. 1b is an XRD pattern of a Cu-Zn-Fe-LDH and peroxide composite (composite oxidant); FIG. 2b is an infrared spectrum of a Cu-Zn-Fe-LDH and peroxide composite (composite oxidant); FIG. 3b is a TEM image of Cu-Zn-Fe-LDH and peroxide composite (composite oxidant).
In order to verify the effect of the composite oxidant in the embodiment of the invention, the decabromodiphenyl oxide is degraded by adopting the synthesized composite oxidant, which specifically comprises the following steps: adding 0.4g/L (concentration after addition) of the composite oxidant into tetrahydrofuran solution of decabromodiphenyl ether with the concentration of 20mg/L, and reacting with H2SO4And regulating the pH value to 2, the ultrasonic power to 400w and the ultrasonic time to 120 minutes, and carrying out degradation. FIG. 4 is a graph showing the efficiency of degradation of polybrominated diphenyl ethers using the oxidizing agent prepared in example 1. Indicating complete degradation within 120 minutes.
In addition, Table 1 shows the measurement data (mg/L) of the oxygen content in water at different times after adding the composite oxidant of the present invention: taking 50mL of water sample, determining the content of dissolved oxygen by a dissolved oxygen determinator, adding 100mg of composite oxidant, standing, determining the content of dissolved oxygen once every 10min 30min, once every 15min 30-60 min, and then once every 30min, comparing the result after standing for 300min with the content of dissolved oxygen in water before adding, and finally judging the oxygen production effect of the composite oxidant. As can be seen from Table 1, the oxygen content in water was low when the complex oxidizer was not added, and gradually increased after the complex oxidizer was added. According to the embodiment of the invention, calcium peroxide in the composite oxidant reacts in water to automatically generate oxygen, the oxygen increasing effect is good, the oxygen amount is increased, and degradation is assisted. Wherein sample 1 is sand lake water; sample 2 is Changjiang river water.
TABLE 1
Figure BDA0002615560280000061
Example 2
Preparing multi-metal hydrotalcite Cu-Zn-Fe-LDH by a coprecipitation method, and controlling the molar ratio of Zn to Fe to Cu to be 1:10:1 respectively. Dissolving nitrates of three metals in water, stirring vigorously, controlling the pH value of the solution to be 7, stirring for 6h in a water bath at 40 ℃, finally aging for 6h, removing a supernatant, centrifuging the lower-layer precipitate for 15min at 5000rpm, washing, and continuously repeating for 3 times to obtain the Cu-Zn-Fe-LDH precipitate.
The oxidant is further synthesized by the following steps: dissolving 1g NaOH solid in 10mL water to form a suspension, and adding 0.1g KH2PO4As a stabilizer, after stirring for 30min, 1mL of 30% H was added2O2The solution is reacted for 15min, if a mixed sample is prepared, 10mL of Cu-Zn-Fe-LDH suspension is added at the moment, the mixture is stirred for 1min until the mixture is uniformly stirred, and H is added2O2And (3) carrying out solution reaction, carrying out suction filtration after reacting for 15min, and drying the upper-layer precipitate at 120 ℃ overnight to obtain the composite material of sodium peroxide and Cu-Zn-Fe-LDH as the composite oxidant.
The method for degrading decabromodiphenyl oxide by adopting the synthesized oxidant specifically comprises the following steps: adding 1g/L (concentration after adding) of the composite oxidant into tetrahydrofuran solution of decabromodiphenyl ether with the concentration of 20mg/L, and reacting with H2SO4And regulating the pH value to be 2, the ultrasonic power to be 100w and the ultrasonic time to be 30 minutes, and carrying out degradation. FIG. 5 is a graph showing the efficiency of degradation of polybrominated diphenyl ethers using the oxidizing agent prepared in this example 2. Indicating complete degradation within 120 minutes.
Example 3
The multi-metal hydrotalcite Cu-Zn-Fe-LDH is prepared by a coprecipitation method, and the molar ratio of Zn to Fe to Cu is respectively controlled to be 10:1: 1. Dissolving nitrates of three metals in water, stirring vigorously, controlling the pH value of the solution to be 6, stirring for 8h in a water bath at 50 ℃, finally aging for 8h, removing a supernatant, centrifuging the lower-layer precipitate for 15min at 5000rpm, washing, and continuously repeating for 3 times to obtain the Cu-Zn-Fe-LDH precipitate.
The oxidant is further synthesized by the following steps: dissolving 10g KOH solid in 50mL water to form a suspension, adding 1g KH2PO4As a stabilizer, after stirring for 40min, 10mL of 30% H was added2O2The solution is reacted for 20min, if a mixed sample is prepared, 100mL of Cu-Zn-Fe-LDH suspension is added at the moment, the mixture is stirred for 10min until the mixture is stirred uniformly, and H is added2O2And (3) carrying out solution reaction, carrying out suction filtration after reacting for 30min, and drying the upper-layer precipitate at 140 ℃ overnight to obtain the composite material of potassium peroxide and Cu-Zn-Fe-LDH as an oxidant.
The method for degrading decabromodiphenyl oxide by adopting the synthesized oxidant specifically comprises the following steps: 2g/L (concentration after addition) of the oxidizing agent was added to a 20mg/L tetrahydrofuran solution of decabromodiphenyl ether, and the mixture was treated with H2SO4The degradation is performed by adjusting the pH to 6, the ultrasonic power to 800w and the ultrasonic time to 120 minutes, and fig. 6 is a schematic diagram of the efficiency of degrading polybrominated diphenyl ethers by using the oxidant prepared in this example 3. Indicating complete degradation within 120 minutes.
Example 4
The multi-metal hydrotalcite Cu-Zn-Fe-LDH is prepared by a coprecipitation method, and the molar ratio of Zn to Fe to Cu is controlled to be 1:1:10 respectively. Dissolving sulfate of three metals in water, stirring vigorously, controlling the pH value of the solution to be 7, stirring for 5h in a water bath at 40 ℃, finally aging for 4h, removing a supernatant, centrifuging the lower-layer precipitate for 15min at 5000rpm, washing, and continuously repeating for 3 times to obtain the Cu-Zn-Fe-LDH precipitate.
The oxidant is further synthesized by the following steps: mixing 5g of Ca (OH)2Dissolving the solid in 20mL water to obtain a suspension, and adding 0.5g KH2PO4As a stabilizer, after stirring for 30min, 5mL of 30% H was added2O2The solution is reacted for 15min, if a mixed sample is prepared, 50mL of Cu-Zn-Fe-LDH suspension is added at the moment, the mixture is stirred for 1min until the mixture is stirred uniformly, and H is added2O2The solution reacts for 15min, then is filtered, the upper layer sediment is taken out and dried overnight at the temperature of 110 ℃, and CaO is obtained2And Cu-Zn-Fe-LDH as an oxidizing agent.
The method for degrading decabromodiphenyl oxide by adopting the synthesized oxidant specifically comprises the following steps: 4g/L (concentration after addition) of the oxidizing agent was added to a 20mg/L tetrahydrofuran solution of decabromodiphenyl ether, and the mixture was treated with H2SO4The degradation was performed by adjusting the pH to 4, the ultrasonic power to 500w, and the ultrasonic time to 60 minutes, and fig. 7 is a schematic diagram showing the efficiency of degrading polybrominated diphenyl ethers by using the oxidizing agent prepared in this example 4. Indicating complete degradation within 120 minutes.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A preparation method of a composite oxidant is characterized by comprising the following steps: the method comprises the following steps:
dissolving hydroxide solid in water to obtain suspension, adding stabilizer, stirring, and adding H2O2Reacting the solution for 10-30min, adding the suspension of the polymetallic hydrotalcite Cu-Zn-Fe-LDH prepared by the coprecipitation method, stirring until the suspension is uniform, and then adding H2O2The solution reacts for 10-30min, solid-liquid separation is carried out after the reaction, and the obtained solid is dried to obtain the composite material of peroxide and Cu-Zn-Fe-LDH as the composite oxidant.
2. The method for preparing the composite oxidant according to claim 1, wherein: the hydroxide solid is selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; correspondingly, the peroxide in the composite material is one or more of sodium peroxide, potassium peroxide and calcium peroxide; the stabilizer is preferably KH2PO4。
3. The method for preparing the composite oxidant according to claim 1, wherein: in the multi-metal hydrotalcite Cu-Zn-Fe-LDH, the molar ratio of Zn to Fe to Cu is controlled to be 1-10:1-10:1-10 respectively.
4. The method for preparing the composite oxidant according to claim 1 or 3, characterized in that: the preparation method of the polymetallic hydrotalcite Cu-Zn-Fe-LDH by the coprecipitation method comprises the following steps: respectively contain Cu2+Salt, containing Zn2+Salts and Fe-containing compounds2+Dissolving salt in water, stirring vigorously, controlling the pH value of the solution to be 6-7, stirring for 1-8h in a water bath at 40-50 ℃, aging for 1-8h, removing supernatant, centrifuging the lower-layer precipitate, and washing to obtain Cu-Zn-Fe-LDH precipitate.
5. The method for preparing a composite oxidant according to any one of claims 1 to 4, wherein: dissolving 1-10g of hydroxide solid in water to form a suspension, and adding 0.1-1g of KH2PO4Stirring for 20-40min, adding 1-10mL of 30% H2O2Reacting the solution for 10-30min, adding 10-100mL Cu-Zn-Fe-LDH suspension, stirring for 1-10min until uniform, and adding H2O2Reacting the solution, filtering after reacting for 10-30min, taking the upper layer precipitate, drying overnight at the temperature of 110-140 ℃ to obtain the composite material of peroxide and Cu-Zn-Fe-LDH, namely the composite oxidant.
6. The composite oxidizing agent produced by the method for producing a composite oxidizing agent according to any one of claims 1 to 5.
7. Use of the composite oxidizing agent prepared by the preparation method according to any one of claims 1 to 5, wherein: under the assistance of an ultrasonic means, the composite oxidant is used for the adsorption and degradation of polybrominated diphenyl ethers.
8. A method for degrading polybrominated diphenyl ethers is characterized by comprising the following steps: the method comprises the following steps: adding the composite oxidant prepared by the preparation method of any one of claims 1 to 5 into an organic solvent solution of polybrominated diphenyl ethers, adjusting the pH to 2 to 6 with acid liquor, and degrading under an ultrasonic state.
9. The degradation method according to claim 9, characterized in that: the mass ratio of the polybrominated diphenyl ether to the composite oxidant is 1:20-1: 200.
10. The degradation method according to claim 8, characterized in that: the polybrominated diphenyl ether is preferably decabrominated diphenyl ether, the ultrasonic power is preferably 100w-800w, and the ultrasonic time is preferably 30-120 minutes.
CN202010768384.7A 2020-08-03 2020-08-03 Preparation method and application of composite oxidant Pending CN112047450A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797873A (en) * 2022-05-11 2022-07-29 华东理工大学 High-activity zinc-iron hydrotalcite heterogeneous Fenton material and method for removing organic pollutants by using same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014132183A1 (en) * 2013-03-01 2014-09-04 Kumar Sumeet "hybrid composite nanomaterials"
CN106179174A (en) * 2016-07-07 2016-12-07 同济大学 For layered composite metal hydroxides removing water pollutant and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014132183A1 (en) * 2013-03-01 2014-09-04 Kumar Sumeet "hybrid composite nanomaterials"
CN106179174A (en) * 2016-07-07 2016-12-07 同济大学 For layered composite metal hydroxides removing water pollutant and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
潘长华: "《实用小化工生产大全 第1卷 无机化工产品 复混肥料 农药 兽药》", 30 September 1999 *
石春蕾等: "水滑石基固体双氧水处理水体中金属络合染料研究", 《工业水处理》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797873A (en) * 2022-05-11 2022-07-29 华东理工大学 High-activity zinc-iron hydrotalcite heterogeneous Fenton material and method for removing organic pollutants by using same

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