CN113788515B - Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application - Google Patents

Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application Download PDF

Info

Publication number
CN113788515B
CN113788515B CN202110832070.3A CN202110832070A CN113788515B CN 113788515 B CN113788515 B CN 113788515B CN 202110832070 A CN202110832070 A CN 202110832070A CN 113788515 B CN113788515 B CN 113788515B
Authority
CN
China
Prior art keywords
cathode material
cosmetic cotton
fenton cathode
heterogeneous electro
fenton
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110832070.3A
Other languages
Chinese (zh)
Other versions
CN113788515A (en
Inventor
朱龙海
段春宁
王广耀
于再基
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Chemical Langzheng Environmental Protection Technology Co ltd
Original Assignee
China Chemical Langzheng Environmental Protection Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Chemical Langzheng Environmental Protection Technology Co ltd filed Critical China Chemical Langzheng Environmental Protection Technology Co ltd
Priority to CN202110832070.3A priority Critical patent/CN113788515B/en
Publication of CN113788515A publication Critical patent/CN113788515A/en
Application granted granted Critical
Publication of CN113788515B publication Critical patent/CN113788515B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices

Abstract

The invention discloses a heterogeneous electro-Fenton cathode material for industrial wastewater treatment and a preparation method and application thereof, wherein the raw materials comprise cosmetic cotton and soluble ferric salt solution; the preparation method comprises the following steps: carrying out ultrasonic treatment on a mixed system comprising cosmetic cotton and a soluble iron salt solution, carrying out hydrothermal reaction at the temperature of 150-250 ℃, carrying out vacuum drying to obtain an electrode material loaded with nano metallic iron, and carrying out vacuum carbonization on the electrode material loaded with the nano metallic iron at the temperature of 100-300 ℃ to obtain the heterogeneous electro-Fenton cathode material. The heterogeneous electro-Fenton cathode material prepared by the method can be applied to the treatment of acidic, neutral and alkaline industrial wastewater, the removal rate of antibiotics in 10min can reach more than 99%, the highest removal rate of TOC mineralization can reach 85%, and the heterogeneous electro-Fenton cathode material has the advantages of high reaction activity and good treatment effect.

Description

Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, a preparation method and application.
Background
Additional H for removing organic matters by Fenton oxidation 2 O 2 And catalyst Fe 2+ The generated hydroxyl free radical with strong oxidizing ability can realize the degradation and even mineralization of organic pollutants, and H with strong corrosion and strong oxidizing property 2 O 2 There are serious transportation and storage safety problems, which bring higher treatment cost and operation risk to the Fenton oxidation removal of organic matters.
In recent years, electro-Fenton for further progress of Fenton oxidationAs technology evolves, the reaction of electro-Fenton technology is based on molecular oxygen (O) 2 ) Reduction to hydrogen peroxide (H) at the cathode 2 O 2 ) And with ferrous ions (Fe) 2+ ) The reaction generates hydroxyl radical (. OH) with strong oxidizing property, thereby realizing the oxidative degradation of the pollutants. The reaction is as follows:
O 2 +2H + +2e - →H 2 O 2 (1)
H 2 O 2 +Fe 2+ →Fe 3+ +·OH+OH - (2)
electro-Fenton oxidation is carried out by adding homogeneous iron ions directly into the solution, however, under neutral and alkaline conditions, fe 3+ Iron sludge precipitate is inevitably formed, so that H generated on the surface of the cathode material 2 O 2 Is difficult to be mixed with Fe in solution 2+ The catalytic reaction to form OH occurs, and this electro-Fenton oxidation method cannot be applied to wastewater treatment in a wide pH range (usually, the most suitable pH is about 3). Therefore, the heterogeneous electro-Fenton cathode material which has a wide pH application range, is especially suitable for near-neutral or alkaline conditions, can efficiently generate OH on the surface of an electrode in situ is developed, and the popularization and the application of the wastewater treatment technology of the electro-Fenton technology are facilitated.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, a preparation method and application aiming at the defects of the prior art. The preparation method of the invention uses the cosmetic cotton and the soluble ferric salt solution as raw materials, and prepares the heterogeneous electro-Fenton cathode material through ultrasound, hydrothermal, vacuum drying and vacuum carbonization, and can be applied to the treatment of acidic, neutral and alkaline industrial wastewater, the removal rate of antibiotics in 10min can reach more than 99%, the highest removal rate of TOC mineralization can reach 85%, and the preparation method has the advantages of high reaction activity and good treatment effect.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that raw materials comprise cosmetic cotton and a soluble iron salt solution;
the preparation method comprises the following steps: carrying out ultrasonic treatment on a mixed system comprising cosmetic cotton and a soluble ferric salt solution, carrying out hydrothermal reaction at the temperature of 150-250 ℃, carrying out vacuum drying to obtain an electrode material loaded with nano metallic iron, and carrying out vacuum carbonization on the electrode material loaded with the nano metallic iron at the temperature of 100-300 ℃ to obtain the heterogeneous electro-Fenton cathode material.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that the hydrothermal reaction time is 4-8 h.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that the vacuum drying temperature is 80-100 ℃, and the vacuum drying time is 8-12 hours.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that a mixed system comprising cosmetic cotton and a soluble iron salt solution is subjected to ultrasonic treatment, and the method specifically comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution soaked with the cosmetic cotton, taking out the cosmetic cotton after the ultrasonic treatment, washing with deionized water, and drying to obtain pretreated cosmetic cotton;
step two, preparing a soluble iron salt solution: dissolving soluble ferric salt in deionized water to obtain a soluble ferric salt solution;
step three, ultrasonic treatment: and (4) placing the pretreated cosmetic cotton in the step one into the soluble iron salt solution in the step two, and carrying out ultrasonic treatment for 30-40 min to obtain an ultrasonic after-treatment system.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that the method for vacuum carbonization of the electrode material loaded with nano metallic iron at the temperature of 100-300 ℃ specifically comprises the following steps: placing the electrode material loaded with the nano metallic iron in a tube furnace, and carrying out argon atmosphere at 2 ℃ for min -1 ～10℃min -1 The temperature rise rate is increased to 100-300 ℃, and the temperature is kept for 1-4 hAnd carrying out vacuum carbonization to obtain the heterogeneous electro-Fenton cathode material.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that in the step one, the mass of the ethanol solution is 3-5 times that of the cosmetic cotton, and the mass percentage of ethanol in the ethanol solution is 75-95%; the ultrasonic frequency of the ethanol solution soaked with the cosmetic cotton is 30 kHz-40 kHz, and the ultrasonic treatment time is 20 min-30 min; the drying temperature in the first step is 60-80 ℃, and the drying time is 8-10 h.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that in the soluble iron salt solution in the second step, the ratio of the mass of the soluble iron salt to the volume of the deionized water is 5: (20-40), wherein the unit of the mass of the soluble ferric salt is mg, and the unit of the volume of the deionized water is mL; the mass of the cosmetic cotton is 15-20 times of that of the soluble ferric salt; the soluble ferric salt is ferric chloride.
The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that the frequency of the ultrasound in the step three is 40 kHz-50 kHz.
In addition, the invention also provides the heterogeneous electro-Fenton cathode material prepared by the method.
Furthermore, the invention also provides a method for applying the heterogeneous electro-Fenton cathode material.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the invention takes the cosmetic cotton and the soluble ferric salt solution as raw materials, and prepares the heterogeneous electro-Fenton cathode material through ultrasound, hydrothermal, vacuum drying and vacuum carbonization, and can be applied to the treatment of acidic, neutral and alkaline industrial wastewater, the removal rate of antibiotics in 10min can reach more than 99%, the highest removal rate of TOC mineralization can reach 85%, and the preparation method has the advantages of high reaction activity, good treatment effect and no iron mud generation.
2. The preparation method of the invention takes the cosmetic cotton as one of the raw materials, has the characteristics of wide selection range of the raw materials of the electrode and high recycling rate of the waste cosmetic cotton pad and other materials, and is beneficial to realizing resource utilization.
3. The preparation method comprises the step of placing the pretreated cosmetic cotton in a soluble ferric salt solution for hydrothermal reaction, so that the in-situ growth of metal nano particles can be effectively promoted, and the defect that the conventional method takes granular materials as electrode raw materials and needs secondary forming is overcome.
4. The preparation method of the invention has low cost and long service life, and is beneficial to popularization and application.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a scanning electron micrograph of the heterogeneous electro-Fenton cathode material of example 1.
FIG. 2 is a scanning electron micrograph of the pretreated cotton pad of step one of example 1.
Fig. 3 is a graph showing the effect of treating an antibiotic-containing system using the heterogeneous electro-fenton cathode material of example 1 as a cathode.
FIG. 4 shows the removal rate of TOC mineralization in the treatment of wastewater of different pH values using the heterogeneous electro-Fenton cathode material of example 1 as a cathode.
FIG. 5 shows the removal rate of TOC mineralization in wastewater treated continuously with the heterogeneous electro-Fenton cathode material of example 1 as cathode.
Detailed Description
The cosmetic cotton is common cosmetic cotton in the market, and the cosmetic cotton manufacturer in the following examples is Xinjiang Tolan cosmetic cotton sheets, the thickness of the sheets is 4mm, and the sizes of the sheets are 4cm multiplied by 8cm.
Example 1
The embodiment provides a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, which comprises the following steps of preparing cosmetic cotton and a soluble ferric salt solution;
the preparation method comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution soaked with the cosmetic cotton, taking out the cosmetic cotton after the ultrasonic treatment, washing with deionized water, and drying to obtain pretreated cosmetic cotton; the mass of the ethanol solution is 5 times of that of the cosmetic cotton, and the mass percentage of the ethanol in the ethanol solution is 80%; the ultrasonic frequency for treating the ethanol solution soaked with the cosmetic cotton is 35kHz, the ultrasonic power is about 150w, the ultrasonic treatment is carried out according to the working rate of 60-80%, and the ultrasonic treatment time is 25min; the drying temperature is 70 ℃, and the drying time is 9 hours;
step two, preparing a soluble iron salt solution: dissolving 5mg of soluble ferric salt in 30mL of deionized water to obtain a soluble ferric salt solution; the mass of the cosmetic cotton in the first step is 18 times of that of the soluble ferric salt in the second step; the soluble ferric salt is ferric chloride;
step three, ultrasonic treatment: placing the pretreated cosmetic cotton in the first step into the soluble ferric salt solution in the second step, and carrying out ultrasonic treatment for 30min to obtain an ultrasonic after-treatment system; the ultrasonic frequency is 45kHz, the ultrasonic power is about 150w, and the ultrasonic operation is carried out according to the work rate of 60-80%;
step four, rapidly transferring the ultrasonic system obtained in the step three into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 6 hours at the temperature of 180 ℃, removing redundant liquid phase, and obtaining the electrode material after the hydrothermal reaction, wherein the volume in the hydrothermal reaction kettle is about 16 times of the mass of ferric chloride, the volume unit in the hydrothermal reaction kettle is mL, and the mass unit of the ferric chloride is mg;
fifthly, drying the electrode material subjected to the hydrothermal reaction in the fourth step in a vacuum drying oven at 90 ℃ for 10 hours to obtain the electrode material loaded with nano metallic iron;
sixthly, placing the electrode material loaded with the nano metallic iron into a tube furnace, and performing argon atmosphere at 5 ℃ for min -1 The temperature rise rate is increased to 300 ℃, and the vacuum carbonization is carried out after 1h, thus obtaining the heterogeneous electro-Fenton cathode material.
Evaluation of Performance
As shown in fig. 1 and 2, it can be seen from fig. 1 and 2 that the heterogeneous electro-fenton cathode material of example 1 and the scanning electron microscope images of the pretreated cotton wool obtained in step one can effectively increase the active sites of the electrode by loading a large amount of metal nanoparticles on the surface of the heterogeneous electro-fenton cathode material.
Application method
The heterogeneous electro-fenton cathode material of example 1 and the cathode material used in the conventional electro-fenton system were used as the cathode, the platinum sheet was the anode, and the contaminant-containing system was the electrolyte, and an evaluation experiment for contaminant removal performance was performed, in which the contaminant-containing system was the antibiotic-containing system, pH was 7, and the initial content of antibiotic in the antibiotic-containing system was 60mg/L. As can be seen from fig. 3, when the heterogeneous electro-fenton cathode material of the present invention is used as a cathode, the removal rate of antibiotics in 10min reaches more than 99%, which is 5 times that of the cathode material used in the conventional electro-fenton system, which indicates that the heterogeneous electro-fenton cathode material of the present invention has stronger electro-catalytic activity and can effectively remove pollutants. The cathode material for the traditional electro-Fenton system is an activated carbon fiber electrode material which is purchased from the market, and the cathode material also comprises a graphite felt electrode material and a carbon cloth electrode material with similar performance.
Taking the heterogeneous electro-Fenton cathode material of example 1 and the cathode material used in the conventional electro-Fenton system as cathodes, platinum sheets as anodes, and the pollutant-containing system as electrolytes, a pollutant removal performance evaluation experiment was performed, wherein the pollutant-containing system is an antibiotic system containing tetracycline, and in the system, the initial content of tetracycline is 60mg/L, and in the antibiotic system containing tetracycline with pH of 3, 5, 7 or 9, the mineralization removal rate of Total Organic Carbon (TOC) is as shown in FIGS. 4 and 5, as can be seen from FIG. 4, when the heterogeneous electro-Fenton cathode material of the present invention is taken as a cathode, the mineralization removal rate of TOC is good in a wide range of pH 3-9, indicating that when the heterogeneous electro-Fenton cathode material of the present invention is taken as a cathode, the mineralization removal rate of TOC for acidic, neutral and alkaline wastewater can be widely applied, and in addition, when the heterogeneous electro-Fenton cathode material of the present invention is taken as a cathode, and the mineralization removal rate of TOC for acidic, neutral and alkaline wastewater can reach 85%, indicating that the heterogeneous electro-Fenton cathode material of the present invention has high efficiency of pollutants in removing pollutants. When the heterogeneous electro-Fenton cathode material is used as a cathode, the removal rate of TOC is over 80% for the same kind of wastewater after continuous operation for 15 times, and the heterogeneous electro-Fenton cathode material is suitable for long-term wastewater treatment and has the characteristic of high stability.
Example 2
The embodiment provides a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, which comprises the following steps of preparing cosmetic cotton and a soluble ferric salt solution;
the preparation method comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution in which the cosmetic cotton is soaked, taking out the cosmetic cotton after the ultrasonic treatment, washing the cosmetic cotton by using deionized water, and drying to obtain pretreated cosmetic cotton; the mass of the ethanol solution is 4 times of that of the cosmetic cotton, and the mass percentage of the ethanol in the ethanol solution is 75%; the ultrasonic frequency for treating the ethanol solution soaked with the cosmetic cotton is 30kHz, the ultrasonic power is about 150w, the ultrasonic treatment is carried out according to the work rate of 60-80%, and the ultrasonic treatment time is 20min; the drying temperature is 60 ℃, and the drying time is 10h;
step two, preparing a soluble iron salt solution: dissolving 5mg of soluble ferric salt in 30mL of deionized water to obtain a soluble ferric salt solution; the mass of the cosmetic cotton in the first step is 15 times of that of the soluble ferric salt in the second step; the soluble ferric salt is ferric chloride;
step three, ultrasonic treatment: placing the pretreated cosmetic cotton in the first step into the soluble ferric salt solution in the second step, and carrying out ultrasonic treatment for 35min to obtain an ultrasonic after-system; the ultrasonic frequency is 40kHz, the ultrasonic power is about 150w, and the ultrasonic generator operates according to the work rate of 60-80%;
step four, rapidly transferring the ultrasonic system obtained in the step three into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at the temperature of 150 ℃, removing redundant liquid phase, and obtaining the electrode material after the hydrothermal reaction, wherein the volume in the hydrothermal reaction kettle is about 12 times of the mass of ferric chloride, the volume unit in the hydrothermal reaction kettle is mL, and the mass unit of the ferric chloride is mg;
fifthly, drying the electrode material subjected to the hydrothermal reaction in the fourth step in a vacuum drying oven at 80 ℃ for 12 hours to obtain the electrode material loaded with the nano metallic iron;
sixthly, loading the nano metalPlacing the iron electrode material in a tube furnace under argon atmosphere at 10 deg.C for min -1 The temperature rise rate is increased to 200 ℃, and the vacuum carbonization is carried out after 3 hours to obtain the heterogeneous electro-Fenton cathode material.
The performance of the heterogeneous electro-Fenton cathode material of this example is substantially the same as that of example 1.
Example 3
The embodiment provides a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, which comprises the following steps of preparing cosmetic cotton and a soluble ferric salt solution;
the preparation method comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution in which the cosmetic cotton is soaked, taking out the cosmetic cotton after the ultrasonic treatment, washing the cosmetic cotton by using deionized water, and drying to obtain pretreated cosmetic cotton; the mass of the ethanol solution is 3 times of that of the cosmetic cotton, and the mass percentage of the ethanol in the ethanol solution is 90%; the ultrasonic frequency for treating the ethanol solution soaked with the cosmetic cotton is 40kHz, the ultrasonic power is about 150w, the ultrasonic treatment is carried out according to the work rate of 60-80%, and the ultrasonic treatment time is 30min; the drying temperature is 80 ℃, and the drying time is 8 hours;
step two, preparing a soluble iron salt solution: dissolving 5mg of soluble ferric salt in 30mL of deionized water to obtain a soluble ferric salt solution; the mass of the cosmetic cotton in the first step is 20 times of that of the soluble ferric salt in the second step; the soluble ferric salt is ferric chloride;
step three, ultrasonic treatment: placing the pretreated cosmetic cotton in the first step into the soluble ferric salt solution in the second step, and carrying out ultrasonic treatment for 40min to obtain an ultrasonic after-system; the ultrasonic frequency is 50kHz, the ultrasonic power is about 150w, and the ultrasonic generator operates according to the work rate of 60-80%;
step four, rapidly transferring the ultrasonic system obtained in the step three into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4 hours at the temperature of 250 ℃, and removing redundant liquid phase to obtain a hydrothermal reaction electrode material, wherein the volume of the hydrothermal reaction kettle is about 15 times of the mass of ferric chloride, the volume unit of the hydrothermal reaction kettle is mL, and the mass unit of the ferric chloride is mg;
fifthly, placing the electrode material subjected to the hydrothermal reaction in the fourth step in a vacuum drying oven at 100 ℃ for drying for 8 hours to obtain the electrode material loaded with nano metallic iron;
sixthly, placing the electrode material loaded with the nano metallic iron in a tube furnace in an argon atmosphere at 2 ℃ for min -1 The temperature rise rate is increased to 100 ℃, and the vacuum carbonization is carried out after 4 hours to obtain the heterogeneous electro-Fenton cathode material.
The performance of the heterogeneous electro-Fenton cathode material of this example is substantially the same as that of example 1.
Example 4
The embodiment provides a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, which comprises the following steps of preparing cosmetic cotton and a soluble ferric salt solution;
the preparation method comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution in which the cosmetic cotton is soaked, taking out the cosmetic cotton after the ultrasonic treatment, washing the cosmetic cotton by using deionized water, and drying to obtain pretreated cosmetic cotton; the mass of the ethanol solution is 4 times of that of the cosmetic cotton, and the mass percentage of the ethanol in the ethanol solution is 75%; the ultrasonic frequency for treating the ethanol solution soaked with the cosmetic cotton is 30kHz, the ultrasonic power is about 150w, the ultrasonic treatment is carried out according to the work rate of 60-80%, and the ultrasonic treatment time is 20min; the drying temperature is 60 ℃, and the drying time is 10 hours;
step two, preparing a soluble iron salt solution: dissolving 5mg of soluble ferric salt in 20mL of deionized water to obtain a soluble ferric salt solution; the mass of the cosmetic cotton in the first step is 15 times of that of the soluble ferric salt in the second step; the soluble ferric salt is ferric chloride;
step three, ultrasonic treatment: placing the pretreated cosmetic cotton in the first step into the soluble ferric salt solution in the second step, and carrying out ultrasonic treatment for 35min to obtain an ultrasonic after-treatment system; the ultrasonic frequency is 50kHz, the ultrasonic power is about 150w, and the ultrasonic generator operates according to the work rate of 60-80%;
step four, rapidly transferring the ultrasonic system obtained in the step three into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at the temperature of 180 ℃, and removing redundant liquid phase to obtain a hydrothermal reaction electrode material, wherein the volume in the hydrothermal reaction kettle is about 12 times of the mass of ferric chloride, the volume unit in the hydrothermal reaction kettle is mL, and the mass unit of the ferric chloride is mg;
fifthly, placing the electrode material subjected to the hydrothermal reaction in the fourth step in a vacuum drying oven at 90 ℃ for drying for 10 hours to obtain the electrode material loaded with nano metallic iron;
sixthly, placing the electrode material loaded with the nano metallic iron in a tube furnace in an argon atmosphere at 10 ℃ for min -1 The temperature rise rate is increased to 200 ℃, and the vacuum carbonization is carried out after 3 hours to obtain the heterogeneous electro-Fenton cathode material.
The performance of the heterogeneous electro-Fenton cathode material of this example is substantially the same as that of example 1.
Example 5
The embodiment provides a preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment, which comprises the following steps of preparing a cosmetic cotton and a soluble iron salt solution;
the preparation method comprises the following steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution soaked with the cosmetic cotton, taking out the cosmetic cotton after the ultrasonic treatment, washing with deionized water, and drying to obtain pretreated cosmetic cotton; the mass of the ethanol solution is 4 times of that of the cosmetic cotton, and the mass percentage of the ethanol in the ethanol solution is 75%; the ultrasonic frequency for treating the ethanol solution soaked with the cosmetic cotton is 30kHz, the ultrasonic power is about 150w, the ultrasonic treatment is carried out according to the work rate of 60-80%, and the ultrasonic treatment time is 20min; the drying temperature is 60 ℃, and the drying time is 10 hours;
step two, preparing a soluble iron salt solution: dissolving 5mg of soluble iron salt in 40mL of deionized water to obtain a soluble iron salt solution; the mass of the cosmetic cotton in the first step is 20 times of that of the soluble ferric salt in the second step; the soluble ferric salt is ferric chloride;
step three, ultrasonic treatment: placing the pretreated cosmetic cotton in the first step into the soluble ferric salt solution in the second step, and carrying out ultrasonic treatment for 35min to obtain an ultrasonic after-system; the ultrasonic frequency is 40kHz, the ultrasonic power is about 150w, and the ultrasonic operation is carried out according to the working rate of 60-80%;
step four, rapidly transferring the ultrasonic system obtained in the step three into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at the temperature of 200 ℃, and removing redundant liquid phase to obtain a hydrothermal reaction electrode material, wherein the volume in the hydrothermal reaction kettle is about 16 times of the mass of ferric chloride, the volume unit in the hydrothermal reaction kettle is mL, and the mass unit of the ferric chloride is mg;
fifthly, drying the electrode material subjected to the hydrothermal reaction in the fourth step in a vacuum drying oven at 80 ℃ for 12 hours to obtain the electrode material loaded with the nano metallic iron;
sixthly, placing the electrode material loaded with the nano metallic iron into a tube furnace, and performing argon atmosphere at 10 ℃ for min -1 The temperature rise rate is increased to 300 ℃, and the vacuum carbonization is carried out after 3 hours, thus obtaining the heterogeneous electro-Fenton cathode material.
The performance of the heterogeneous electro-Fenton cathode material of this example is substantially the same as that of example 1.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (9)

1. A preparation method of a heterogeneous electro-Fenton cathode material for industrial wastewater treatment is characterized in that raw materials comprise cosmetic cotton and a soluble iron salt solution;
the preparation method comprises the following steps: carrying out ultrasonic treatment on a mixed system comprising cosmetic cotton and a soluble ferric salt solution, carrying out hydrothermal reaction at the temperature of 150-250 ℃, carrying out vacuum drying to obtain an electrode material loaded with nano metallic iron, and carrying out vacuum carbonization on the electrode material loaded with the nano metallic iron at the temperature of 100-300 ℃ to obtain a heterogeneous electro-Fenton cathode material; the time of the hydrothermal reaction is 4 to 8h.
2. The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 1, wherein the temperature of vacuum drying is 80-100 ℃, and the time of vacuum drying is 8h to 12h.
3. The method for preparing the heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 1, wherein the method for performing ultrasonic treatment on the mixed system comprising the cosmetic cotton and the soluble iron salt solution comprises the following specific steps:
step one, pretreating cosmetic cotton: soaking the cosmetic cotton in an ethanol solution, performing ultrasonic treatment on the ethanol solution in which the cosmetic cotton is soaked, taking out the cosmetic cotton after the ultrasonic treatment, washing the cosmetic cotton by using deionized water, and drying to obtain pretreated cosmetic cotton;
step two, preparing a soluble iron salt solution: dissolving soluble ferric salt in deionized water to obtain a soluble ferric salt solution;
step three, ultrasonic treatment: and (4) placing the pretreated cosmetic cotton in the step one in the soluble iron salt solution in the step two, and carrying out ultrasonic treatment for 30min to 40min to obtain an ultrasonic system.
4. The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 1, wherein the vacuum carbonization method of the electrode material loaded with the nano metallic iron at a temperature of 100 ℃ to 300 ℃ specifically comprises: placing the electrode material loaded with the nano metallic iron in a tube furnace under the argon atmosphere at 2 ℃ for min -1 ~10 °C min -1 The temperature rise rate is increased to 100-300 ℃, and vacuum carbonization is carried out for 1h-4h to obtain the heterogeneous electro-Fenton cathode material.
5. The preparation method of the heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 3, wherein the mass of the ethanol solution in the step one is 3-5 times that of the cosmetic cotton, and the mass percentage of ethanol in the ethanol solution is 75% -95%; step one, processing the ethanol solution soaked with the cosmetic cotton, wherein the ultrasonic frequency is 30kHz to 40kHz, and the ultrasonic processing time is 20min to 30min; the drying temperature in the first step is 60-80 ℃, and the drying time is 8-10 h.
6. The method for preparing a heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 3, wherein in the soluble iron salt solution in the second step, the ratio of the mass of the soluble iron salt to the volume of the deionized water is 5: (20 to 40), wherein the unit of the mass of the soluble ferric salt is mg, and the unit of the volume of the deionized water is mL; the mass of the cosmetic cotton is 15-20 times of that of the soluble ferric salt; the soluble ferric salt is ferric chloride.
7. The method for preparing a heterogeneous electro-Fenton cathode material for industrial wastewater treatment according to claim 3, wherein the frequency of the ultrasound in the step three is 40kHz to 50kHz.
8. A heterogeneous electro-fenton cathode material prepared by the method of claim 1.
9. A method for applying the heterogeneous electro-fenton cathode material according to claim 8, wherein said application is to apply said heterogeneous electro-fenton cathode material to acidic, neutral and alkaline industrial wastewater treatment with antibiotic removal rate of above 99% for 10min and TOC mineralization removal rate of 85%.
CN202110832070.3A 2021-07-22 2021-07-22 Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application Active CN113788515B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110832070.3A CN113788515B (en) 2021-07-22 2021-07-22 Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110832070.3A CN113788515B (en) 2021-07-22 2021-07-22 Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application

Publications (2)

Publication Number Publication Date
CN113788515A CN113788515A (en) 2021-12-14
CN113788515B true CN113788515B (en) 2023-02-21

Family

ID=78876897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110832070.3A Active CN113788515B (en) 2021-07-22 2021-07-22 Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application

Country Status (1)

Country Link
CN (1) CN113788515B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114455673A (en) * 2021-12-31 2022-05-10 东华工程科技股份有限公司 Preparation method and application of nano-catalyst-supported electro-Fenton cathode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Flow-through heterogeneous electro-Fenton system based on the absorbent cotton derived bulk electrode for refractory organic pollutants treatment";Xin Wang等;<Separation and Purification Technology>;20210710;第1383-5866页 *

Also Published As

Publication number Publication date
CN113788515A (en) 2021-12-14

Similar Documents

Publication Publication Date Title
WO2018023912A1 (en) Indium-doped titanium-based lead dioxide electrode, and manufacturing method thereof and application of same
CN102887567B (en) Method for modifying graphite felt material applied to electro-Fenton system
CN106745529B (en) TiO 22electro-Fenton-like working cathode for electro-catalytically activating hydrogen peroxide and preparation method and application thereof
CN108675382B (en) Based on TiO2Integrated catalytic system of nanotube photocatalyst and degradation treatment method thereof
CN111533223A (en) FeS2Cathode heterogeneous electro-Fenton water treatment method
CN103641212A (en) Method for preparing graphite felt cathode material for treating organic wastewater
CN111422953A (en) In-situ flocculation-Fenton coupling electrochemical method for advanced treatment of high-salinity wastewater
CN113788515B (en) Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application
CN111054341A (en) Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode
CN114014412B (en) Preparation method and application of cobalt-nitrogen co-doped porous carbon graphite felt electrode
CN112794413B (en) Preparation method and application of graphite felt electrode applied to electro-active PDS system modified bimetal
CN113896299A (en) electro-Fenton reaction cathode material of ferromanganese layered double hydroxide loaded biochar and preparation method and application thereof
CN112142168A (en) Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method
CN111672511A (en) Method for preparing gamma-ferric oxide/silicon dioxide photo-Fenton catalyst composite film layer on titanium alloy surface and application
CN104671362A (en) Electrode for removing bromate in water and preparation method thereof
CN113998760B (en) Copper-cobalt oxide/carbon nano tube/foam nickel composite electrode for heterogeneous electro-Fenton system and application
CN110801826A (en) Photoelectrocatalysis graphite felt material and preparation method and application thereof
CN114455673A (en) Preparation method and application of nano-catalyst-supported electro-Fenton cathode material
CN115072845A (en) Nano porous carbon modified graphite felt cathode material and preparation method and application thereof
CN113896298A (en) electro-Fenton method for in-situ hydrogen peroxide generation or organic pollutant degradation of composite cathode by combining cathode aeration and cathode modification
CN114057224A (en) Preparation method of titanium dioxide, preparation method and application of titanium-based titanium dioxide electrode
CN115925056B (en) Preparation of phosphorus-doped titanium dioxide/titanium foam electrode and method for treating heavy metal wastewater by using phosphorus-doped titanium dioxide/titanium foam electrode
CN114506909B (en) Iron-containing graphene oxide modified graphite felt electrode and preparation method and application thereof
CN116062850B (en) Reinforced Fe 2+ Concentration of bifunctional MoS 2 GF composite cathode, photoelectric Fenton system and application thereof
CN111977939B (en) Method for treating excess sludge dehydration by electrocatalysis coupling sulfate radical free radical

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant