Porous particulate electrode material, method for its production and use thereof

Abstract

The application discloses a kind of porous particle electrode materials and its preparation method and application, preparation method includes that furnace slag, pore former and waste ternary battery filler are added into solution, the solution is acid solution or alkali solution, granulation is carried out using one-step granulation method, then is calcined at 250 DEG C~650 DEG C, obtain porous particle electrode material.The porous particle electrode material prepared in the application is porous structure, and has strong structural stability, and can be applied to enhance electrically activated persulfate degradation sulfonamide wastewater, can provide higher specific surface area and more active sites for electrode, promote the adsorption of persulfate, thereby accelerating the activation of persulfate, accelerate the oxidative degradation of sulfonamide, and have good application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of environmental electrochemistry, and relates to a porous particle electrode material, a preparation method and application thereof, in particular to a porous particle electrode material with strong structural stability and a preparation method and application thereof in enhancing electro-activated persulfate degradation of sulfonamide wastewater. BACKGROUND

[0002] Antibacterial drugs are a kind of drugs used in the fields of livestock, medical treatment and aquaculture to treat and prevent bacterial infections. Excessive use of antibacterial drugs will inhibit and interfere with the growth and reproduction of aquatic organisms in water bodies, and cause many serious environmental problems such as bacterial drug resistance and biological toxicity. Such substances often enter the water environment again with excreta. At present, the technologies for treating antibacterial drug wastewater include biological method, physical-chemical method, chemical method and the like. The biological method usually needs additional nutrients and proper environmental conditions to meet the growth of microorganisms, and therefore is not suitable for removing antibacterial drug pollution in wastewater. The physical-chemical method mainly includes ion exchange and reverse osmosis, but both of them only separate antibacterial drugs from water, and the high-concentration antibacterial drug wastewater produced needs further treatment. The chemical method commonly used is catalytic hydrogenation method, but the production, transportation and preservation of hydrogen gas are also a big problem currently faced. Compared with the above methods, the electro-catalytic oxidation technology has the characteristics of mild reaction conditions, no secondary pollution, flexibility, simplicity and controllability for water treatment. However, this technology also faces some challenges, for example, ① many particle electrodes developed at present are solid, and the internal catalytically active sites do not work, resulting in that catalysis only occurs on the surface thereof; ② many particle electrode materials have poor structural stability; and ③ the preparation cost of particle electrode materials is high.

[0003] In view of this, it is necessary to provide a new type of particle electrode material with strong structural stability and low cost, so as to solve or at least alleviate the defects of high cost, poor structural stability and solidification of particle electrodes. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the defects of the prior art, in particular the defects of high cost, poor structural stability and solidification of particle electrodes, and to provide a porous particle electrode material with strong structural stability and low cost, a preparation method and application thereof.

[0005] To solve the above technical problems, the following technical solutions are adopted in the present application.

[0006] The preparation method of the porous particle electrode material comprises the following steps: adding slag, pore-forming agent and waste ternary battery filler into a solution, the solution being an acid solution or an alkali solution, granulating by using a one-step granulation method, and then calcining at 250 DEG C to 650 DEG C to obtain the porous particle electrode material.

[0007] The preparation method of the porous particle electrode material, preferably, the ratio of the slag, the pore-forming agent, the waste ternary battery filler and the solution is 100.0g-50.0g:0.1g-1.0g:1.0g-10.0g:10mL-30mL.

[0008] The preparation method of the porous particle electrode material, preferably, the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution and nitric acid solution, the mass fraction of acid in the acid solution is 5%-10%, and the temperature of the acid solution is 50°C-80°C; the alkali solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water, the mass fraction of alkali in the alkali solution is 5%-10%, and the temperature of the alkali solution is 50°C-80°C.

[0009] The preparation method of the porous particle electrode material, preferably, the slag contains 10%-30% mass fraction of iron oxide and 30%-45% mass fraction of aluminum oxide, and the particle size of the slag is 200-600 meshes; the pore-forming agent is one or more of graphite powder, activated carbon powder, paraffin, calcium carbonate and ammonium bicarbonate; the waste ternary battery filler contains nickel-cobalt-manganese-lithium with a mass fraction of more than 90% or nickel-cobalt-aluminum-lithium with a mass fraction of more than 90%, and the particle size of the waste ternary battery filler is 200-600 meshes.

[0010] The preparation method of the porous particle electrode material, preferably, the calcination time is 1h-6h.

[0011] The preparation method of the porous particle electrode material, preferably, the particle size of the porous particle electrode material is 0.1cm-1cm, and the pore size is 10nm-30nm.

[0012] The preparation method of the porous particle electrode material, more preferably, the particle size of the porous particle electrode material is 0.35cm-0.65cm.

[0013] As a general technical concept, the application also provides a porous particle electrode material prepared by the preparation method of the porous particle electrode material.

[0014] As a general technical concept, the application also provides an application of the porous particle electrode material in enhancing the degradation of sulfonamide wastewater by electro-activated persulfate.

[0015] The application further relates to a method for enhancing electro-activated persulfate to degrade sulfonamide wastewater, which comprises the following steps: taking a ruthenium iridium titanium plate as an anode, taking a stainless steel plate as a cathode, adding the porous particle electrode material into an electrolytic tank containing sulfonamide wastewater, an electrolyte and a catalyst, adjusting a pH value to be 4-10, and carrying out a reaction under a constant current condition. 2 2 .

[0016] Compared with the prior art, the application has the following advantages:

[0017] 1. The preparation method of the application realizes the characteristics of the porous structure, high structural stability and low cost of the porous particle electrode material through precise design and synthesis of materials, one-step granulation, synergistic effect of three materials of slag, waste ternary battery filler and pore-forming agent, and precise control of the amount of the pore-forming agent, the addition amount of the slag and the ratio of the catalytically active material (waste ternary battery filler).

[0018] At present, many particle electrodes have the disadvantages of solidification, poor structural stability, small specific surface area and high cost. The porous particle electrode material prepared by the application has the following characteristics: low material cost (waste-to-resource), simple electrode preparation process, good degradation effect and strong structural stability. These characteristics are conducive to the wide application of the porous particle electrode material of the application in wastewater containing sulfonamide pollution, such as municipal wastewater, groundwater and industrial wastewater.

[0019] 2. The porous particle electrode material of the application can be applied to enhance electro-activated persulfate to degrade sulfonamide wastewater. The porous structure characteristics of the porous particle electrode material can provide the electrode with higher specific surface area and more active sites, promote the adsorption of persulfate (PMS), and thus facilitate the generation of more active oxygen substances. The characteristics of high structural stability and low cost of the porous particle electrode material are conducive to the promotion of the industrial application process. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The scanning electron microscope image of the porous particle electrode material prepared for the embodiment 1 of the application.​

[0021] Figure 2 Effect diagram of the porous particle electrode material prepared for the present application embodiment 1 in the degradation of sulfonamide wastewater by electro-activated persulfate at different current densities for 1.5h.

[0022] Figure 3 Effect comparison diagram of the porous particle electrode material prepared for different amounts of pore-forming agent in the present application embodiment 2 in the degradation of sulfonamide wastewater by electro-activated persulfate for 1.5h.

[0023] Figure 4 Effect comparison diagram of the porous particle electrode material in the present application embodiment 3 in the degradation of sulfonamide wastewater by electro-activated persulfate for 10 cycles.

[0024] Figure 5 Effect diagram of the porous particle electrode material in the present application embodiment 4 in the degradation of sulfonamide wastewater from the environmental protection workshop of a Changsha pharmaceutical company by electro-activated persulfate for 1.5h.

[0025] Figure 6 Effect diagram of the degradation of sulfonamide wastewater by electro-activated persulfate for 1.5h without the porous particle electrode material in the present application comparative example 1. DETAILED DESCRIPTION

[0026] The present application will be further described in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present application is not limited thereby. In the following embodiments, if not specifically stated, the materials and instruments used are commercially available, the processes used are conventional processes, the equipment used is conventional equipment, and the data obtained are the average values of more than three repeated experiments.

[0027] Embodiment 1

[0028] A preparation method of a porous particle electrode material of the present application, comprising the following steps:

[0029] (1) 100g of slag was soaked in a dilute hydrochloric acid solution containing 0.5g of pore-forming agent and 10g of waste ternary battery filler, the pore-forming agent was ammonium bicarbonate, the slag contained 20wt% of iron oxide and 45wt% of aluminum oxide, the particle size of the slag was 400 mesh, the waste ternary battery filler contained 92wt% of nickel-cobalt-aluminum-lithium, the particle size of the waste ternary battery filler was 450 mesh, the volume of the dilute hydrochloric acid solution was 30mL, the mass fraction of hydrochloric acid in the dilute hydrochloric acid solution was 5%, the temperature of the dilute hydrochloric acid solution was 55℃, and the soaking time was 2h. The obtained mixture was granulated in a granulator, and then the obtained spherical particles were calcined in a muffle furnace at 550℃ for 2h to obtain a porous particle electrode material, the particle size of which was 0.45cm-0.55cm, and the pore size was 10nm-30nm. Figure 1It can be seen that in the porous particle electrode material prepared in Embodiment 1, the catalytically active metal substances (cobalt, nickel, and manganese) in the waste ternary battery are uniformly loaded on the surface of the particle electrode, and in addition, the surface of the particle electrode is rough and has many pore structures.

[0030] The application of the porous particle electrode material of the present embodiment in enhancing the degradation of sulfonamide wastewater by electro-activated persulfate includes the following steps:

[0031] S1, prepare a cathode plate and an anode plate, the cathode plate is a stainless steel plate with a size of 10 cm x 10 cm x 0.2 cm, and the anode plate is a commercial electrode ruthenium iridium titanium plate with a size of 10 cm x 10 cm x 0.2 cm, in an electrolytic cell, sulfonamide wastewater, electrolyte, and catalyst are sequentially added, the concentration of sulfonamide in the sulfonamide wastewater is 100 mg / L, the volume of the sulfonamide wastewater is 200 mL, the electrolyte is anhydrous sodium sulfate, the molar concentration of the electrolyte in the sulfonamide wastewater is 0.25 mmol / L, and the catalyst is potassium hydrogen persulfate composite salt (purity greater than 98%, Shanghai Titan Science and Technology Co., Ltd.), and the molar concentration of the catalyst in the sulfonamide wastewater is 0.30 mmol / L;

[0032] S2, adjust the pH value of the above wastewater to 7.0 by using dilute hydrochloric acid and dilute sodium hydroxide solution, then place 50 g of the porous particle electrode material in the above electrolytic cell, and degrade for 1.5 h under a constant current condition with a current density of 6, 8, 10, 12, and 14 mA / cm 2 , and the results are shown in Figure 2 .

[0033] As can be seen from Figure 2 , in the present embodiment, when the current density increases from 6 mA / cm 2 to 14 mA / cm 2 , the removal efficiency of sulfonamide increases from 74.12% to 99.98%, which indicates that the increase of the current density can enhance the degradation performance of sulfonamide, but when the current density exceeds 12 mA / cm 2 , the degradation efficiency no longer changes.

[0034] Embodiment 2

[0035] A preparation method of the porous particle electrode material of the present embodiment includes the following steps:

[0036] (1) 100 g of slag containing 20 wt% of iron oxide and 45 wt% of aluminum oxide was immersed in a dilute hydrochloric acid solution containing 0 g, 0.25 g, 0.5 g, 0.75 g, and 1.0 g of ammonium bicarbonate and 10 g of waste ternary battery filler containing 92% of nickel, cobalt, aluminum, and lithium by mass, the particle size of the slag was 400 mesh, the particle size of the waste ternary battery filler was 450 mesh, the mass fraction of hydrochloric acid in the dilute hydrochloric acid solution was 5%, the volume of the dilute hydrochloric acid solution was 30 mL, the temperature of the dilute hydrochloric acid solution was 55°C, and the immersion time was 2 h. The obtained mixture was granulated in a granulator and then calcined in a muffle furnace at 550°C for 2 h to obtain a porous particle electrode material with a particle size of 0.45 cm to 0.55 cm and a pore size of 10 nm to 30 nm. Table 1 is the specific surface area of the porous particle electrode material under different ammonium bicarbonate dosing conditions in this example.

[0037] Table 1: Specific surface area of the porous particle electrode material under different ammonium bicarbonate dosing conditions

[0038]

[0039]

[0040] A porous particle electrode material of this example (different amounts of pore-forming agent were added during preparation) was applied to enhance the degradation of sulfonamide wastewater by electrically activated persulfate, and the process was basically the same as in Example 1, except that the sulfonamide wastewater was degraded by electrically activated persulfate under a constant current condition with a current density of 12 mA / cm 2 for 1.5 h, and the results are shown in Figure 3 .

[0041] As can be seen from Table 1 and Figure 3 , the specific surface area of the porous particle electrode material increases with the increase of the pore-forming agent ammonium bicarbonate, and the degradation efficiency of sulfonamide also increases with the increase of the pore-forming agent ammonium bicarbonate, but the specific surface area and sulfonamide removal rate hardly change when the amount of ammonium bicarbonate exceeds 0.5 g. Therefore, the optimal dosing amount of ammonium bicarbonate is 0.5 g.

[0042] Example 3

[0043] A porous particle electrode material of this example and a method for preparing the same are the same as in Example 1.

[0044] A porous particle electrode material of this example was applied to enhance the degradation of sulfonamide wastewater by electrically activated persulfate, and the process was basically the same as in Example 1, except that the sulfonamide wastewater was degraded by electrically activated persulfate under a constant current condition with a current density of 12 mA / cm 2The porous particle electrode material was repeatedly electrocatalytically degraded for ten times under the same degradation process conditions after the electro-activated persulfate was used to degrade the sulfonamide wastewater for 1.5 h under the constant current condition of 12 mA / cm

[0045] Table 2 Mass loss rate of the porous particle electrode material after being recycled for ten times

[0046] Cycle number Mass (g) Mass loss rate (%) 0 50.0 0 1 49.715 0.57 2 49.505 0.99 3 49.29 1.42 4 49.08 1.84 5 48.7 2.26 6 48.66 2.68 7 48.445 3.11 8 48.245 3.51 9 48.035 3.93 10 47.825 4.35

[0047] Figure 4 The application of the porous particle electrode material of the present embodiment to enhance the effect of electro-activated persulfate on the degradation of sulfonamide for ten times is shown in the comparison chart. The sulfonamide removal rate only decreased from 99.98% to 99.63% after being recycled for ten times, indicating that the porous particle electrode material has excellent stability. In addition, as shown in Table 2, the mass loss rate of the 50 g material only decreased by 4.35% after being recycled for ten times. Based on the above data, it can be concluded that the porous particle electrode material of the present application has good structural stability.

[0048] Example 4

[0049] The porous particle electrode material of the present application and the preparation method thereof are the same as those of Example 1.

[0050] The application of the porous particle electrode material of the present embodiment to enhance the effect of electro-activated persulfate on the degradation of sulfonamide for ten times is shown in the comparison chart. The sulfonamide removal rate only decreased from 99.98% to 99.63% after being recycled for ten times, indicating that the porous particle electrode material has excellent stability. In addition, as shown in Table 2, the mass loss rate of the 50 g material only decreased by 4.35% after being recycled for ten times. Based on the above data, it can be concluded that the porous particle electrode material of the present application has good structural stability.

[0051] S1, prepare the cathode plate and the anode plate, the cathode uses a 10 cm x 10 cm x 0.2 cm stainless steel plate, the anode uses a commercial electrode ruthenium iridium titanium plate with a size of 10 cm x 10 cm x 0.2 cm, and 200 mL of sulfonamide wastewater from the environmental protection workshop of a Changsha pharmaceutical company, electrolyte and catalyst are sequentially added in the electrolytic cell, wherein the concentration of sulfonamide in the sulfonamide wastewater is 125.6 mg / L, the electrolyte is anhydrous sodium sulfate, the molar concentration of the electrolyte in the sulfonamide wastewater is 0.25 mmol / L, and the catalyst is potassium hydrogen persulfate composite salt (purity above 98%, Shanghai Titan Science and Technology Co., Ltd.), the molar concentration of the catalyst in the sulfonamide wastewater is 0.30 mmol / L.

[0052] S2, adjust the pH value of the above wastewater to 7.0 by using dilute hydrochloric acid and dilute sodium hydroxide solution, then place 50 g of the porous particle electrode material in the above electrolytic cell, and degrade for 1.5 h under the constant current condition of 12 mA / cm 2 Figure 5 Figure 5 As shown in Table 2, the removal rate of sulfonamide and the removal rate of TOC (total organic carbon) in the wastewater reached 98.65% and 50.26%, respectively. ​​

[0053] Based on the above results, it can be seen that the porous particle electrode material prepared by this invention has a good degradation efficiency for both simulated wastewater and real wastewater, indicating that the porous particle electrode material has strong potential for industrial application.

[0054] Comparative Example 1

[0055] A method for electro-activated persulfate degradation of sulfonamide wastewater is basically the same as the application process in Example 1, except that: without the porous particle electrode material of Example 1, at a current density of 12 mA / cm² 2 Under constant current conditions, the persulfate was electroactivated to degrade sulfonamide wastewater for 1.5 h, and the results were as follows: Figure 6 As shown.

[0056] Depend on Figure 6 It is known that when electro-activated persulfate degrades sulfonamide wastewater, the degradation efficiency without porous particle electrode material drops significantly from 99.98% to 52.21%. Therefore, it can be seen that the porous particle electrode material of the present invention can indeed enhance the performance of electric field activated persulfate degradation of sulfonamide.

[0057] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the spirit and technical essence of the present invention. Therefore, any simple modifications, equivalent substitutions, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention shall still fall within the protection scope of the technical solutions of the present invention.

Claims

1. A method for producing a porous particulate electrode material, characterized by, The method comprises the following steps: The slag, pore-forming agent and waste ternary battery filler are added into a solution, which is an acid solution or an alkali solution, granulated by one-step granulation method, and then calcined at 250-650 DEG C to obtain a porous particle electrode material; The ratio of the slag, pore-forming agent, waste ternary battery filler and solution is 100.0-50.0 g:0.1-1.0 g:1.0-10.0 g:10-30 mL; The slag contains 10-30% of iron oxide and 30-45% of aluminum oxide by mass fraction, and the waste ternary battery filler contains more than 90% of nickel-cobalt-manganese-lithium by mass fraction or more than 90% of nickel-cobalt-aluminum-lithium by mass fraction.

2. The method of claim 1, wherein the porous particulate electrode material is prepared by a process comprising: The acid solution is one or more of sulfuric acid solution, hydrochloric acid solution and nitric acid solution, the mass fraction of acid in the acid solution is 5-10%, and the temperature of the acid solution is 50-80 DEG C; the alkali solution is one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water, the mass fraction of alkali in the alkali solution is 5-10%, and the temperature of the alkali solution is 50-80 DEG C.

3. The method of claim 1, wherein the porous particulate electrode material is prepared by a process comprising: The particle size of the slag is 200-600 meshes; the pore-forming agent is one or more of graphite powder, activated carbon powder, paraffin, calcium carbonate and ammonium bicarbonate; and the particle size of the waste ternary battery filler is 200-600 meshes.

4. The method of claim 1 to 3, wherein The calcination time is 1-6 h.

5. The method of claim 1-3, wherein the porous particulate electrode material is prepared by a process comprising: The particle size of the porous particle electrode material is 0.1-1 cm, and the pore size is 10-30 nm.

6. The method of claim 5, wherein the porous particulate electrode material is prepared by a process comprising: The particle size of the porous particle electrode material is 0.35-0.65 cm. 7.A porous particle electrode material prepared by the method of any one of claims 1-6. 8.The porous particle electrode material of claim 7 is used for enhancing the degradation of sulfonamide wastewater by electro-activated persulfate.

9. Use according to claim 8, characterized in that, The application comprises the following steps: taking a ruthenium iridium titanium plate as an anode, a stainless steel plate as a cathode, adding the porous particle electrode material into an electrolytic tank containing sulfonamide wastewater, electrolyte and catalyst, adjusting the pH value to 4-10, and carrying out the reaction under constant current condition to enhance the electro-activated persulfate degradation of sulfonamide wastewater; the mass concentration of sulfonamide in the sulfonamide wastewater is 50 mg / L-200 mg / L, the electrolyte is one or more of sodium chloride, anhydrous sodium sulfate and sodium nitrate, the molar concentration of the electrolyte in the sulfonamide wastewater is 0.25 mmol / L-1.0 mmol / L, the catalyst is at least one of potassium hydrogen persulfate, sodium hydrogen persulfate, potassium hydrogen persulfate composite salt and sodium hydrogen persulfate composite salt, the molar concentration of the catalyst in the sulfonamide wastewater is 0.10 mmol / L-0.75 mmol / L, the mass ratio of the porous particle electrode material to the volume of the sulfonamide wastewater is 20 g-50 g: 150 mL-200 mL, and the current density used in the constant current condition is 6 mA / cm 2 -20 mA / cm 2 .

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