Preparation of modified dielectric rubber material and its application in water treatment field

Abstract

The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment. The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment. The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment. The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment. The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment. The application discloses a preparation method of modified dielectric rubber material and application of the modified dielectric rubber material in water treatment, and belongs to the technical field of water treatment.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalytic materials, and relates to preparation of modified dielectric rubber and application thereof in the field of water treatment. The application provides an application of ultrasonic driving to realize contact electrocatalytic activation of oxidants for degrading organic pollutants in water, and relates to a new degradation mechanism of organic pollutants. Rubber belongs to dielectric materials, and has the advantages of high wear resistance, good elasticity, acid and alkali resistance, and strong comprehensive performance. Due to the excellent dielectric property, the rubber is more likely to produce electron transfer in the process of tribocharging, improves the transmission capacity of electrons, and is beneficial to the activation of oxidants and the generation of more free radicals for degrading organic pollutants.

BACKGROUND TECHNIQUE

[0002] Pollutants containing antibiotics, hormones, antibacterial agents, dyes and various organic components have caused potential risks to the ecological system and human health due to their continuous discharge, and have attracted great attention in recent years. Water treatment has been paid attention to. At present, water treatment can be solved through piezoelectric catalysis, photocatalysis, electrochemical oxidation and Fenton and other advanced oxidation processes. In the field of antibiotic degradation, various catalytic processes have been greatly developed. However, the problems of high preparation cost, difficult preparation and stability of the catalyst are highlighted. Therefore, emerging catalytic methods gradually enter people's field of vision. With the help of the tribocharging mechanism of dielectric materials, contact electrocatalysis enters people's field of vision. The cavitation bubbles generated by ultrasonic frequently contact the material surface to produce static charges. These static charges can undergo electron transfer with the medium in the environment, thereby triggering various oxidation-reduction reactions, i.e. contact electrocatalysis.

[0003] Patent CN115957643A discloses a device for water-solid contact electrocatalytic degradation of trace antibiotics using high-charge-density nanofiber membranes. The prepared high-charge-density nanofiber membranes are assembled into an ultrasonic filtration unit, then wastewater containing trace antibiotics and suspended particles is introduced into the ultrasonic wave chamber from the water inlet pipe, and the high-frequency vibration of ultrasonic promotes the generation of cavitation bubbles in the wastewater. The cavitation bubbles from generation to rupture make the wastewater and nanofiber membranes frequently contact and tribocharge, and produce contact electrocatalytic effect to degrade trace antibiotics flowing through the membrane holes. Patent CN111847498A discloses a cadmium sulfide nanorod and a method for tribo-catalytic degradation of organic pollutants. The piezoelectric property of the cadmium sulfide with a specific structure enables it to more effectively accumulate mechanical energy in the environment. Under light-free conditions, only through magnetic stirring, the degradation of organic matter can be realized, overcoming the problem of low visible light response efficiency in conventional photocatalytic experiments. However, the traditional material preparation has the problems of high cost, poor stability and low recycling times of the material.

[0004] The modified dielectric rubber material is used in the present application, which is beneficial to electron transfer in activating oxidant, improves catalytic efficiency, and is easy to recycle and does not cause secondary pollution. SUMMARY

[0005] [PROBLEMS TO BE SOLVED BY THE INVENTION]

[0006] The present application aims to solve the problems of powder catalytic material in the field of catalysis, such as difficult recycling, easy to cause secondary pollution, low catalytic efficiency, high cost and instability of catalyst preparation, and the modified dielectric rubber material can overcome these shortcomings and has high material stability and catalytic performance.

[0007] [TECHNICAL SCHEME]

[0008] 1. (1) Prepare four conical flasks, first, respectively, take 8.1 g of anhydrous ferric chloride, 6.8 g of zinc chloride, 8.0 g of anhydrous copper sulfate and 9.2 g of cobalt nitrate according to the same amount of substance (0.05 mol) and add them into four conical flasks, and then add 200 mL of deionized water to dissolve at room temperature; then add 4-8 g of dielectric rubber catalyst to each of the four conical flasks and soak for 48 hours.

[0009] (2) After soaking, pour the remaining solution into four beakers respectively for standby; the modified material is washed with deionized water for three times until no color is shown after washing, and then put into a constant temperature drying oven and dry at 80℃ for 1 hour to obtain the modified dielectric rubber material.

[0010] (3) According to the standard of 0.05 mol / L of the amount of substance concentration, take the corresponding mass of oxidant powder and add it to a 50 mL beaker containing deionized water to stir and dissolve.

[0011] (4) Select three organic pollutants, tetracycline, levofloxacin and rhodamine B, and respectively take 10 mg of solid powder and add it to a 1000 mL beaker to stir for 6 hours, and then make up to 1000 mL in a volumetric flask.

[0012] 2. (1) Prepare four 200 mL beakers in advance, first, respectively, take 8.1 g of anhydrous ferric chloride, 6.8 g of zinc chloride, 8.0 g of anhydrous copper sulfate and 9.2 g of cobalt nitrate according to the same amount of substance (0.05 mol) and add them into four conical flasks, and then add 200 mL of deionized water to dissolve at room temperature.

[0013] (2) Add natural rubber to the beaker containing organic solvent, heat under water bath condition at 80-95℃ for 60-90 minutes to dissolve and obtain solution I.

[0014] (3) Mix solution I with three kinds of inorganic salt solution according to the volume ratio of 1:1-1:3 to obtain mixed solution II.

[0015] (4) Use a syringe or rubber dropper to take 2-3 mL of solution II each time and drop into the deionized water containing the surfactant to coagulate, after coagulation, pour the water into a constant temperature drying oven and dry at 80℃ for 1-2 hours to obtain modified dielectric rubber material B.

[0016] (5) Select three organic pollutants, tetracycline, levofloxacin and rhodamine B, and weigh 10 mg of solid powder into a 1000 mL beaker, each for 6 hours, and then dilute to 1000 mL in a volumetric flask.

[0017] The rubber doped with metal ions has metal elements on the surface.

[0018] The oxidizing agent can be peroxymonosulfate and peroxodisulfate, and the dielectric rubber material triggers electron transfer under the action of ultrasound to activate the oxidizing agent for water treatment.

[0019] The dielectric rubber doped with metal cations has better effect on activating the oxidizing agent than the same amount of metal ions activating the oxidizing agent.

[0020] The organic solvent includes toluene, xylene, N,N-dimethylformamide, etc.

[0021] The contact electrically activated oxidizing agent is driven by ultrasound, and the cavitation bubbles generated by ultrasound are in frequent friction contact with the surface of the dielectric rubber material, which improves the electron transfer ability to activate the oxidizing agent, and further generates more free radicals to degrade organic pollutants.

[0022] The organic pollutants are tetracycline, levofloxacin and rhodamine B.

[0023] [Advantages]

[0024] Rubber is a widely concerned dielectric material in the field of contact electrocatalytic water treatment, and excellent dielectric performance is conducive to electron transfer. Excellent contact electrocatalyst. Compared with the prior art, the advantages and beneficial effects of the present application are:

[0025] (1) The modified dielectric rubber material in the present application has high wear resistance, elasticity and acid and alkali resistance.

[0026] (2) The modified dielectric rubber material prepared by the present application has simple preparation process, low cost and easy to be applied in large scale.

[0027] (3) The dielectric catalytic material prepared by the present application has the advantages of high recovery rate, not easy to secondary pollution, high stability and high catalytic activity, which is conducive to the demand of large-scale water treatment.

DRAWINGS

[0028] Figure 1 This is a SEM image of the surface of the modified dielectric rubber material A prepared after the implementation scheme.

[0029] Figure 2 This is a SEM image of the surface of the modified dielectric rubber material B prepared after the implementation scheme.

[0030] Figure 3 The degradation curves of pollutants in water after contact electrocatalytic degradation are shown in the figure.

Detailed Implementation Methods

[0031] Example 1:

[0032] (1) Prepare an Erlenmeyer flask in advance, and mix anhydrous ferric chloride particles with deionized water in a mass (g) to volume (mL) ratio of 2:200 in the Erlenmeyer flask to obtain a ferric solution with a concentration of 10 g / L.

[0033] (2) Add 4g of dielectric rubber catalyst to the conical flask and soak for 24 hours.

[0034] (3) After soaking, pour the remaining solution into a beaker for later use; rinse the modified material three times with deionized water until there is no color after rinsing, and then put it in a constant temperature drying oven and dry it at 80°C for 1 hour to obtain the modified dielectric rubber material.

[0035] (4) Weigh 0.77g of potassium persulfate powder according to the standard concentration of 0.05mol / L and add it to a beaker containing 50mL of deionized water and stir to dissolve.

[0036] (5) Weigh 10 mg of tetracycline solid powder and add it to a beaker. Stir for 6 hours and then dilute to a volumetric flask with a volume of 1000 mL.

[0037] (6) Take the modified dielectric rubber material prepared in (3), measure 100 mL of the tetracycline solution prepared in (5), and put them together in a 500 mL beaker. Drive the tetracycline solution by ultrasound (ultrasound frequency of 40 kHz) to degrade the tetracycline solution. Take the solution at different times and measure the concentration of tetracycline.

[0038] Example 2:

[0039] (1) Prepare an Erlenmeyer flask in advance, and mix anhydrous ferric chloride particles with deionized water in a mass (g) to volume (mL) ratio of 4:200 in the Erlenmeyer flask to obtain a ferric solution with a concentration of 20 g / L.

[0040] (2) Add 6g of dielectric rubber catalyst to the conical flask and soak for 36 hours.

[0041] (3) After the soaking is completed, pour the remaining solution into a beaker for standby use; the modified material is washed with deionized water for three times until no color is shown after washing, and then is placed into a constant-temperature drying oven to be dried at a temperature of 80°C for 1.5 hours to obtain the modified dielectric rubber material.

[0042] (4) 0.77 g of potassium persulfate powder is weighed according to the standard of 0.05 mol / L of the concentration of substance of matter, and is added into a beaker containing 50 mL of deionized water to be stirred and dissolved.

[0043] (5) 10 mg of solid levofloxacin powder is weighed and added into the beaker to be stirred for 6 hours, and then is diluted to a 1000 mL volumetric flask.

[0044] (6) The modified dielectric rubber material prepared in (3) is taken, 100 mL of the levofloxacin solution prepared in (5) is measured, and both are placed into a 500 mL beaker to be driven by ultrasonic waves (the frequency of the ultrasonic waves is 80 kHz) to degrade the levofloxacin solution. The solution at different time points is sucked to measure the concentration of levofloxacin.

[0045] Example 3:

[0046] (1) A conical flask is prepared in advance, and anhydrous ferric chloride particles and deionized water are mixed and dissolved in the conical flask according to the ratio of 6:200 of mass (g) to volume (mL) to obtain a trivalent iron solution with a concentration of 30 g / L.

[0047] (2) 8 g of dielectric rubber catalyst is added into the conical flask and soaked for 48 hours.

[0048] (3) After the soaking is completed, pour the remaining solution into a beaker for standby use; the modified material is washed with deionized water for three times until no color is shown after washing, and then is placed into a constant-temperature drying oven to be dried at a temperature of 80°C for 2 hours to obtain the modified dielectric rubber material.

[0049] (4) 0.77 g of potassium persulfate powder is weighed according to the standard of 0.05 mol / L of the concentration of substance of matter, and is added into a beaker containing 50 mL of deionized water to be stirred and dissolved.

[0050] (5) 10 mg of solid rhodamine B powder is weighed and added into the beaker to be stirred for 6 hours, and then is diluted to a 1000 mL volumetric flask.

[0051] (6) The modified dielectric rubber material prepared in (3) is taken, 100 mL of the tetracycline solution prepared in (5) is measured, and both are placed into a 500 mL beaker to be driven by ultrasonic waves (the frequency of the ultrasonic waves is 100 kHz) to degrade the rhodamine B solution. The solution at different time points is sucked to measure the concentration of rhodamine B.

Claims

1. An application of a modified dielectric rubber material in water treatment, characterized in that, The method for preparing the modified dielectric rubber material. Includes the following steps: (1) Preparation of modified dielectric rubber material A: 1) Prepare four conical flasks. Weigh out 8.1 g of anhydrous ferric chloride, 6.8 g of zinc chloride, 8.0 g of anhydrous copper sulfate and 9.2 g of cobalt nitrate into the four conical flasks respectively, and add 200 mL of deionized water to dissolve them at room temperature. Then add 4-8 g of dielectric rubber material to each of the four conical flasks and soak for 48 hours. 2) The modified material was rinsed three times with deionized water until no color was visible after rinsing, and then placed in a constant temperature drying oven and dried at 80°C for 1 hour to obtain modified dielectric rubber material A. (2) Preparation of modified dielectric rubber material B: 1) Prepare four 200 mL beakers in advance. Weigh out 8.1 g of anhydrous ferric chloride, 6.8 g of zinc chloride, 8.0 g of anhydrous copper sulfate, and 9.2 g of cobalt nitrate into four conical flasks, and dissolve them in 200 mL of deionized water at room temperature. 2) Add natural rubber to a beaker containing organic solvent and heat in a water bath at 80-95°C for 60-90 minutes to dissolve it, thus obtaining solution I; 3) Mix solution I with four inorganic salt solutions in a volume ratio of 1:1 to 1:3 to obtain mixed solution II; 4) Use a syringe or dropper to take 2-3 mL of solution II each time and add it to deionized water containing surfactant to solidify. After solidification, pour off the water and put it in a constant temperature drying oven at 80℃ for 1-2 hours to obtain modified dielectric rubber material B. (3) Select an oxidant and place it together with the prepared modified dielectric rubber material A or B into a beaker, and decompose organic pollutants under ultrasonic drive; The oxidizing agent is persulfate and perdisulfate.

2. The application of the modified dielectric rubber material according to claim 1 in water treatment, characterized in that, The organic solvents used include toluene, xylene, and N,N-dimethylformamide.

3. The application of the modified dielectric rubber material according to claim 1 in water treatment, characterized in that, The oxidant concentration is 0.05 mol / L.

4. The application of the modified dielectric rubber material according to claim 1 in water treatment, characterized in that, The organic pollutants are tetracycline, levofloxacin, and rhodamine B, and the ultrasonic frequency is 40 kHz-100 kHz.

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