CN106809921B - Preparation method of kaolin-based three-dimensional particle electrode - Google Patents
Preparation method of kaolin-based three-dimensional particle electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a kaolin-based three-dimensional particle electrode, which comprises the following steps: (1) grinding: grinding kaolin and hydrilla verticillata into powder, and drying to constant weight;(2) mixing and forming: dissolving ferrous sulfate heptahydrate and copper sulfate pentahydrate in water to obtain a mixed solution, putting kaolin powder and hydrilla verticillata powder into the mixed solution, performing equal-volume impregnation and adsorption for 1-3h, and uniformly mixing to prepare small balls with the particle size of 3-5 mm; (3) and (3) drying: drying the pellets; (4) and (3) calcining: and calcining the pellets to obtain the kaolin-based particle electrode. The kaolin-based particle electrode prepared by the method, which is provided by the invention, takes kaolin with a porous structure as a carrier and hydrilla verticillata as a pore-forming agent, and loads a Fe and Cu bimetallic catalyst on the kaolin particle electrode, wherein the load-type particle electrode can provide homogeneous Fe for reaction2+And Cu2+The catalyst and the heterogeneous Fenton catalyst have good degradation effect on the dye wastewater and can be recycled.
Description
Technical Field
The invention relates to the field of environmental protection and treatment, in particular to a preparation method of a kaolin-based three-dimensional particle electrode.
Background
The dye is widely applied to daily life, especially in the industries of printing and dyeing, printing, spinning, cosmetics and the like. The dye wastewater has the characteristics of complex pollutant components, deep chromaticity, difficult degradation, high toxicity and the like, and can cause serious harm to human bodies and aquatic organisms if the dye wastewater is directly discharged without treatment. The traditional water treatment process at present is difficult to obtain ideal effect on dye wastewater. Therefore, it is necessary to study the treatment techniques of such substances.
Electrochemistry is used as a green water treatment technology and is widely applied to the control of organic pollutants difficult to degrade. The three-dimensional electrode is formed by filling granular or other crumbly electrode materials between two electrodes of a traditional two-dimensional electrode to form a plurality of micro-electrolysis cells, and electrochemical reaction is carried out on the surface of a working electrode material. Compared with a two-dimensional electrode, the three-dimensional electrode has the advantages that the surface area ratio is greatly increased, the particle spacing is reduced, and the mass transfer effect is improved. But as an electrochemical technology, the energy consumption is still higher than that of the common advanced oxidation technology, and in the aspect of practical application, the current efficiency is improved, the treatment cost is reduced, and the electrochemical technology can be widely applied to wastewater treatment.
The electro-Fenton technology is to generate H in a reaction system by utilizing electrochemistry2O2Therefore, a Fenton reaction occurs to oxidize the organic matter, but the traditional electric Fenton method has the defects of difficult control of the addition amount of ferrous salt, narrow pH application range and the like. At present, the Fenton reaction can be promoted and the applicable range of pH can be increased based on the introduction of other transition metals such as Cu salt. However, the traditional electro-Fenton technology has the defects that a large amount of iron mud is generated after the reaction is finished, the catalyst cannot be recycled, and the like, so that the application of the catalyst is limited.
The three-dimensional electrode/electro-Fenton technology organically couples the three-dimensional electrode method and the Fenton method, loads a Fenton catalyst on a particle electrode, can be used as a heterogeneous Fenton catalyst and also used as a particle electrode, simultaneously carries out three-dimensional electrode electro-catalysis and Fenton reaction in the same reactor, has the reaction advantages of the three-dimensional electrode electro-catalysis and the Fenton reaction, forms a synergistic effect, overcomes the defects of small electrode surface area, difficult recovery, poor mass transfer effect, narrow pH application range and the like of the traditional electro-Fenton method, and greatly improves the current efficiency and the space-time yield per unit.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a kaolin-based three-dimensional particle electrode, and the prepared particle electrode can be used as a heterogeneous Fenton catalyst and can also be used as a three-dimensional electrode, so that the particle electrode has the advantages of high catalytic activity, wide pH application range, reusability and the like.
In order to achieve the above object, the present invention provides a method for preparing a kaolin-based three-dimensional particle electrode, comprising the steps of:
(1) grinding: grinding kaolin and hydrilla verticillata into powder, and then drying to constant weight;
(2) mixing and forming: dissolving ferrous sulfate heptahydrate and copper sulfate pentahydrate in water to obtain a mixed solution, putting the kaolin powder and the hydrilla verticillata powder prepared in the step (1) into the mixed solution, and performing equal-volume impregnation and adsorption for 1-3h to uniformly mix the kaolin powder and the hydrilla verticillata powder to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the pellets prepared in the step (2);
(4) and (3) calcining: and (4) calcining the pellets dried in the step (3) to obtain the kaolin-based particle electrode.
Preferably, in the above technical solution, the temperature for drying in the step (1) is 80-120 ℃.
Preferably, in the above technical solution, in the step (2), the content of Fe, which is an active component of the ferrous sulfate heptahydrate, is 0.5 to 3 wt% of the electrode mass of the kaolin-based particles.
Preferably, in the above technical solution, the copper sulfate pentahydrate in the step (2) has an active component Cu content of 0.5-3 wt% of the mass of the kaolin-based particle electrode.
Preferably, in the above technical scheme, the mass ratio of the kaolin powder to the hydrilla verticillata powder in the step (2) is 1.5-4: 1.
Preferably, in the above technical solution, the drying in the step (3) is performed at a temperature of 80-120 ℃ for 12-24 h.
Preferably, in the above technical solution, the calcination in the step (4) is performed at 450-750 ℃.
Preferably, in the above technical solution, the calcination in the step (4) is performed by raising the temperature to 750 ℃ at a temperature-raising rate of 5 ℃/min, and then calcining at constant temperature for 300min and 120-.
The method for treating dye wastewater utilizes the kaolin-based particle electrode prepared by the method to treat dye wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) the kaolin-based particle electrode prepared by the preparation method of the kaolin-based three-dimensional particle electrode adopts the kaolin which is non-toxic, pollution-free, cheap and easily available and has a porous structure as a carrier and the hydrilla verticillata as a pore-forming agent, and the Fe and Cu bimetallic catalyst is loaded on the kaolin particle electrode, and the loaded particle electrode can provide homogeneous Fe for reaction2+And Cu2 +The catalyst and the heterogeneous Fenton catalyst solve the problems that the adding amount of the traditional Fenton-like catalyst is not easy to control and is troublesome to operate, the catalyst is difficult to recover, the current efficiency is low and the like in the traditional electro-Fenton catalyst, have a good degradation effect on dye wastewater, and can be recycled.
(2) The prepared particle electrode has large specific surface area and good conductivity and catalytic performance, is a novel kaolin-based particle electrode, greatly increases the reaction area of the electrode, improves the reaction speed of the electrode, and can efficiently degrade dye wastewater.
(3) The kaolin-based particle electrode can provide homogeneous and heterogeneous Fenton catalysts, and solves the problems that the dosage of the traditional electro-Fenton catalyst is not easy to control, the operation is troublesome, the pH application range is small, the cost is high, the catalyst is difficult to recover and the like.
(4) The kaolin-based particle electrode loads Fe and Cu active components with catalytic function on the kaolin particle electrode, so that the specific surface of the catalyst is greatly improved, the loss of the Fe and Cu active components is avoided, the service life of the particle electrode is prolonged, and the kaolin-based particle electrode can be repeatedly utilized.
(5) The preparation method is simple and feasible, and is easy to popularize in a large range.
Drawings
Fig. 1 is an SEM image of the kaolin-based three-dimensional particle electrode prepared by the method of preparing the kaolin-based three-dimensional particle electrode of example 1.
Fig. 2 is an EDS energy spectrum of the kaolin-based three-dimensional particle electrode prepared by the method of preparing the kaolin-based three-dimensional particle electrode of example 1.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The principle of the preparation method of the kaolin-based three-dimensional particle electrode is that a novel three-dimensional electrode/electric Fenton method is adopted, the three-dimensional electrode method and the electric Fenton method are coupled, direct oxidation of an anode and the particle electrode, generation of OH indirect oxidation of the anode and the particle electrode and generation of Fe generated by the particle electrode can be simultaneously carried out2+And Cu2+And active sites of heterogeneous Fenton catalyst on the surface of the particle electrode, and H generated by the cathode2O2The Fenton reaction is a comprehensive electrochemical oxidation technology with a plurality of functions. Compared with the traditional electro-Fenton technology, the method has the advantages of increased surface area ratio, small particle spacing, enlarged pH application range, easy catalyst recovery and the like.
Example 1
A preparation method of a kaolin-based three-dimensional particle electrode comprises the following steps:
(1) grinding: firstly, grinding kaolin by using a ball mill, then grinding the kaolin into fine powder by using a mortar as much as possible, sieving the powder by using a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 80 ℃ to obtain constant weight; then, grinding the hydrilla verticillata by using a ball mill, grinding kaolin into fine powder as much as possible by using a mortar, sieving the powder by using a 80-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 120 ℃ to constant weight;
(2) mixing and forming: 0.7446g (0.5 wt% of Fe) ferrous sulfate heptahydrate and 0.5859g (0.5 wt% of Cu) copper sulfate pentahydrate are dissolved in 20mL deionized water, 18g of pretreated kaolin powder and 12g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for equal-volume impregnation and adsorption for 1h, and the materials are uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: the pellets prepared above are dried in a constant temperature drying oven at 120 ℃ for 24 h.
(4) And (3) calcining: and (3) placing the dried pellets in a muffle furnace, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 300min to obtain the kaolin-based particle electrode. The morphology of the prepared particle electrode is shown in figure 1.
The three-dimensional electrode reactor was prepared by filling the kaolin-based particle electrode prepared in the above example into a reactor with 30g/L of graphite plates and stainless steel plates as the anode and cathode, respectively. The test was carried out at pH 3, voltage 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of degradation time and removal rate are shown in Table 1, and it can be seen from Table 1 that 92.26% removal rate can be achieved after 60min treatment.
TABLE 1 results of removal rate of rhodamine B by the kaolin-based particle electrode obtained in example 1
| Time/ |
10 | 20 | 30 | 40 | 50 | 60 |
| Removal rate/%) | 36.82 | 50.96 | 65.37 | 72.41 | 85.69 | 92.46 |
Example 2
A preparation method of a kaolin-based three-dimensional particle electrode comprises the following steps:
(1) grinding: firstly, grinding kaolin by using a ball mill, then grinding the kaolin into fine powder by using a mortar as much as possible, sieving the powder by using a 100-mesh molecular sieve, and placing the powder in a constant-temperature drying box to be dried at the temperature of 100 ℃ and to be constant in weight; then, grinding the hydrilla verticillata by using a ball mill, grinding kaolin into fine powder as much as possible by using a mortar, sieving the powder by using a 80-mesh molecular sieve, and placing the powder in a constant-temperature drying box to be dried at the temperature of 100 ℃ and be subjected to constant weight;
(2) mixing and forming: 1.4892g (1.0 wt% of Fe) ferrous sulfate heptahydrate and 1.1718g (1.0 wt% of Cu) copper sulfate pentahydrate are dissolved in 20mL deionized water, pretreated 21.0g of kaolin powder and 9.0g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for isovolumetric immersion and adsorption for 3h, and the materials are uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 120 ℃ for 24 hours;
(4) and (3) calcining: and (3) placing the dried pellets in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 120min to obtain the kaolin-based particle electrode.
The three-dimensional electrode reactor was prepared by filling the kaolin-based particle electrode prepared in the above example into a reactor with 30g/L of graphite plates and stainless steel plates as the anode and cathode, respectively. Test at pH 3, electricPressure 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of degradation time and removal rate are shown in Table 2, and it can be seen from Table 2 that the removal rate of 98.63% can be achieved after 60min treatment.
Table 2 results of removal rate of the kaolin-based particle electrode on rhodamine B obtained in example 2
| Time/ |
10 | 20 | 30 | 40 | 50 | 60 |
| Removal rate/%) | 48.5 | 66.3 | 86.9 | 91.54 | 95.52 | 98.63 |
Example 3
A preparation method of a kaolin-based three-dimensional particle electrode comprises the following steps:
(1) grinding: firstly, grinding kaolin by using a ball mill, then grinding the kaolin into fine powder by using a mortar as much as possible, sieving the powder by using a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 80 ℃ to obtain constant weight; then, grinding the hydrilla verticillata by using a ball mill, grinding kaolin into fine powder as much as possible by using a mortar, sieving the powder by using a 80-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 120 ℃ to constant weight;
(2) mixing and forming: 2.9784g (2.0 wt% of Fe) ferrous sulfate heptahydrate and 2.3436g (2.0 wt% of Cu) copper sulfate pentahydrate are dissolved in 20mL deionized water, pretreated 24.0g of kaolin powder and 6.0g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for equal-volume impregnation and adsorption for 2h, and the mixture is uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 100 ℃ for 18 h;
(4) and (3) calcining: and (3) placing the dried pellets in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 180min to obtain the kaolin-based particle electrode.
The three-dimensional electrode reactor was prepared by filling the kaolin-based particle electrode prepared in the above example into a reactor with 30g/L of graphite plates and stainless steel plates as the anode and cathode, respectively. The test was carried out at pH 3, voltage 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of degradation time and removal rate are shown in Table 3, and it can be seen from Table 3 that 97.52% removal rate was achieved after 60min treatment.
Table 3 results of removing rate of the kaolin-based particle electrode obtained in example 3 to rhodamine B
| Time/ |
10 | 20 | 30 | 40 | 50 | 60 |
| Removal rate/%) | 46.81 | 68.25 | 79.15 | 85.24 | 92.37 | 97.52 |
Example 4
A preparation method of a kaolin-based three-dimensional particle electrode comprises the following steps:
(1) grinding: firstly, grinding kaolin by using a ball mill, then grinding the kaolin into fine powder by using a mortar as much as possible, sieving the powder by using a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 80 ℃ to obtain constant weight; then, grinding the hydrilla verticillata by using a ball mill, grinding kaolin into fine powder as much as possible by using a mortar, sieving the powder by using a 80-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 120 ℃ to constant weight;
(2) mixing and forming: 4.4676g (3.0 wt% of Fe) ferrous sulfate heptahydrate and 3.5154g (3.0 wt% of Cu) copper sulfate pentahydrate are dissolved in 20mL deionized water, pretreated 21.0g of kaolin powder and 9.0g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for isovolumetric impregnation and adsorption for 3h, and the mixture is uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 100 ℃ for 18 h;
(4) and (3) calcining: and (3) placing the dried pellets in a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 240min to obtain the kaolin-based particle electrode.
The three-dimensional electrode reactor was prepared by filling the kaolin-based particle electrode prepared in the above example into a reactor with 30g/L of graphite plates and stainless steel plates as the anode and cathode, respectively. The test was carried out at pH 3, voltage 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of degradation time and removal rate are shown in Table 4, and it can be seen from Table 4 that 91.62% removal rate was achieved after 60min treatment.
Table 4 results of removing rate of the kaolin-based particle electrode obtained in example 4 to rhodamine B
| Time/ |
10 | 20 | 30 | 40 | 50 | 60 |
| Removal rate/%) | 46.80 | 58.21 | 68.29 | 71.36 | 85.71 | 91.62 |
Example 5
A preparation method of a kaolin-based three-dimensional particle electrode comprises the following steps:
(1) grinding: firstly, grinding kaolin by using a ball mill, then grinding the kaolin into fine powder by using a mortar as much as possible, sieving the powder by using a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 80 ℃ to obtain constant weight; then, grinding the hydrilla verticillata by using a ball mill, grinding kaolin into fine powder as much as possible by using a mortar, sieving the powder by using a 80-mesh molecular sieve, and drying the powder in a constant-temperature drying box at 120 ℃ to constant weight;
(2) mixing and forming: 2.9784g (2.0 wt% of Fe) ferrous sulfate heptahydrate and 1.1718g (1.0 wt% of Cu) copper sulfate pentahydrate are dissolved in 20mL deionized water, 18.0g of pretreated kaolin powder and 12.0g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for equal-volume impregnation and adsorption for 2h, and the mixture is uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 120 ℃ for 24 hours;
(4) and (3) calcining: and (3) placing the dried pellets in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 240min to obtain the kaolin-based particle electrode.
The three-dimensional electrode reactor was prepared by filling the kaolin-based particle electrode prepared in the above example into a reactor with 30g/L of graphite plates and stainless steel plates as the anode and cathode, respectively. The test was carried out at pH 3, voltage 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of degradation time and removal rate are shown in Table 5, and it can be seen from Table 5 that 93.25% removal rate was achieved after 60min treatment.
Table 5 results of removing rate of the kaolin-based particle electrode obtained in example 5 on rhodamine B
| Time/ |
10 | 20 | 30 | 40 | 50 | 60 |
| Removal rate/%) | 31.08 | 49.25 | 52.89 | 72.57 | 85.63 | 93.25 |
Example 6
Blank kaolin, Fe/kaolin and Cu/kaolin particle electrodes are prepared to serve as reference particle electrodes, the prepared Fe-Cu/kaolin particle electrodes and the reference particle electrodes are subjected to an electrolysis experiment, and the prepared Fe-Cu/kaolin particle electrodes are inspected to have high electrocatalytic activity.
1. The preparation method of the blank kaolin particle electrode comprises the following steps:
(1) grinding: grinding kaolin by a ball mill, grinding the kaolin into fine powder by a mortar as much as possible, sieving the powder by a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying oven at 80 ℃ to constant weight; grinding hydrilla verticillata with a ball mill, grinding kaolin into fine powder with a mortar, sieving with a 80-mesh molecular sieve, and drying in a constant-temperature drying oven at 120 ℃ to constant weight;
(2) mixing and forming: adding the treated kaolin powder 21.0g and the treated hydrilla verticillata powder 9.0g into 20mL of deionized water, and preparing into small balls with the particle size of 3-5mm after uniformly mixing;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 120 ℃ for 24 hours;
(4) and (3) calcining: and (3) placing the dried pellets into a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 120min to obtain the blank kaolin particle electrode.
2. The preparation method of the Fe/kaolin particle electrode comprises the following steps:
(1) grinding: grinding kaolin by a ball mill, grinding the kaolin into fine powder by a mortar as much as possible, sieving the powder by a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying oven at 80 ℃ to constant weight; grinding hydrilla verticillata with a ball mill, grinding kaolin into fine powder with a mortar, sieving with a 80-mesh molecular sieve, and drying in a constant-temperature drying oven at 120 ℃ to constant weight;
(2) mixing and forming: 1.4892g (1.0 wt% of Fe) ferrous sulfate heptahydrate is dissolved in 20mL deionized water, 21.0g of pretreated kaolin powder and 9.0g of hydrilla verticillata powder are put into the mixed solution of the ferrous sulfate heptahydrate and the copper sulfate pentahydrate for equal-volume impregnation and adsorption for 3h, and the materials are uniformly mixed to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 120 ℃ for 24 hours;
(4) and (3) calcining: and (3) placing the dried pellets into a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 120min to obtain the Fe/kaolin particle electrode.
3. The preparation method of the Cu/kaolin particle electrode comprises the following steps:
(1) grinding: grinding kaolin by a ball mill, grinding the kaolin into fine powder by a mortar as much as possible, sieving the powder by a 100-mesh molecular sieve, and drying the powder in a constant-temperature drying oven at 80 ℃ to constant weight; grinding hydrilla verticillata with a ball mill, grinding kaolin into fine powder with a mortar, sieving with a 80-mesh molecular sieve, and drying in a constant-temperature drying oven at 120 ℃ to constant weight;
(2) mixing and forming: 1.1718g (1.0 wt% Cu) of blue vitriod is dissolved in 20mL of deionized water, 21.0g of pretreated kaolin powder and 9.0g of black algae powder are put into the mixed solution of ferrous sulfate heptahydrate and blue vitriod, and equal-volume impregnation and adsorption are carried out for 3h, so that the mixture is uniformly mixed to prepare small balls with the grain diameter of 3-5 mm;
(3) and (3) drying: drying the prepared pellets in a constant-temperature drying oven at 120 ℃ for 24 hours;
(4) and (3) calcining: and (3) placing the dried pellets into a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, and calcining at constant temperature for 120min to obtain the Cu/kaolin particle electrode.
4. The preparation method of the Fe-Cu/kaolin particle electrode is the same as that of example 2.
The blank kaolin, Fe/kaolin and Cu/kaolin particle electrodes and Fe-Cu/kaolin particle electrodes prepared in the above example 6 were filled in a reactor in an amount of 30g/L using a graphite plate and a stainless steel plate as an anode and a cathode, respectively, to prepare a three-dimensional electrode reactor. The test was carried out at pH 3, voltage 10V, electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of the rhodamine B removal rate at 60min for the different particle electrodes are shown in Table 6.
Table 6 results of the removal rate of rhodamine B by the particle electrode prepared in example 6
| Particle electrode | Blank kaoline | Fe/kaolin | Cu/Kaolin | Fe-Cu/Kaolin |
| Removal rate% | 62.05 | 80.16 | 72.84 | 98.63 |
As can be seen from Table 6, the removal rate of the Fe-Cu/kaolin particle electrode prepared by the method is higher than that of the blank kaolin, Fe/kaolin and Cu/kaolin particle electrode in electrocatalysis efficiency.
Example 7:
testing of kaolin-based particle electrodes at different pH conditions:
the kaolin-based particle electrode prepared in the above example 2 was charged and filled in a reactor in an amount of 30g/L using a graphite plate and a stainless steel plate as an anode and a cathode, respectively, to prepare a three-dimensional electrode reactor. The test is carried out at pH 3-9, voltage 10V, and electrolyte Na2SO4The concentration is 5g/L, and the aeration amount is 0.8L/min, 400mL of rhodamine B solution with the concentration of 20mg/L is degraded by electrification for 60 min. The results of the removal rate of rhodamine B by the kaolin-based particle electrode under different pH conditions and with a reaction time of 60min are shown in table 7.
Table 7 results of the removal rate of rhodamine B by the particle electrode prepared in example 7
| pH | 3.0 | 5.0 | 6.65 | 9.0 |
| Removal rate% | 98.63 | 93.51 | 95.72 | 91.48 |
From table 7, it can be seen that the removal rate of rhodamine B of the kaolin-based particle electrode prepared by the present invention reaches 90% under the condition that the pH is 3 to 9, which indicates that the kaolin-based particle electrode has a relatively large pH application range.
Example 8:
stability test of kaolin-based particle electrodes:
the kaolin-based particle electrode prepared in the above example 2 was charged and filled in a reactor in an amount of 30g/L using a graphite plate and a stainless steel plate as an anode and a cathode, respectively, to prepare a three-dimensional electrode reactor. The test was carried out at pH 6.65, voltage 10V, electrolyte Na2SO4And (3) carrying out power-on degradation on 400mL of rhodamine B solution with the concentration of 20mg/L for 60min under the conditions that the concentration is 5g/L and the aeration rate is 0.8L/min, then simply filtering the solution, washing the separated particle electrode with deionized water, drying, and then carrying out an electrocatalytic degradation test under the same conditions. Repeating for 3 times continuously, and measuring the electrode degradation rate of the kaolin-based particles as follows: 97.15%, 93.28%, 90.715%. Therefore, after the kaolin-based particle electrode prepared by the method is recycled for 3 times, the removal rate of rhodamine B is maintained to be more than 90%, which shows that the kaolin isThe base particle electrode has high stability and good reusability.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (3)
1. A preparation method of a kaolin-based three-dimensional particle electrode is characterized by comprising the following steps:
(1) grinding: grinding kaolin and hydrilla verticillata into powder, and then drying to constant weight;
(2) mixing and forming: dissolving ferrous sulfate heptahydrate and copper sulfate pentahydrate in water to obtain a mixed solution, putting the kaolin powder and the hydrilla verticillata powder prepared in the step (1) into the mixed solution, and performing equal-volume impregnation and adsorption for 1-3h to uniformly mix the kaolin powder and the hydrilla verticillata powder to prepare small balls with the particle size of 3-5 mm;
(3) and (3) drying: drying the pellets prepared in the step (2);
(4) and (3) calcining: calcining the pellets dried in the step (3) to obtain the kaolin-based particle electrode;
in the step (2), the mass ratio of the kaolin powder to the hydrilla verticillata powder is 1.5-4: 1; the content of the active component Fe of the ferrous sulfate heptahydrate is 0.5 to 3 weight percent of the mass of the kaolin-based particle electrode; the active component Cu content of the copper sulfate pentahydrate is 0.5 to 3 weight percent of the mass of the kaolin-based particle electrode;
the drying in the step (3) is drying for 12-24h at the temperature of 80-120 ℃;
the calcination in the step (4) is carried out at the temperature of 450-750 ℃, the calcination is carried out at the temperature rising rate of 5 ℃/min to the temperature of 450-750 ℃, and then the calcination is carried out at the constant temperature for 300 min.
2. The method for preparing a kaolin-based three-dimensional particle electrode according to claim 1, wherein the temperature for drying in the step (1) is 80-120 ℃.
3. A method for treating dye wastewater, characterized in that the kaolin-based particle electrode prepared according to claim 1 is used to treat dye wastewater.
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