CN107697984B - Sn/Sb-Mn-GAC particles and application thereof in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater - Google Patents

Sn/Sb-Mn-GAC particles and application thereof in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater Download PDF

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CN107697984B
CN107697984B CN201711132892.0A CN201711132892A CN107697984B CN 107697984 B CN107697984 B CN 107697984B CN 201711132892 A CN201711132892 A CN 201711132892A CN 107697984 B CN107697984 B CN 107697984B
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chlorophenol
gac
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CN107697984A (en
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李媚
廖安平
覃琴
陈熠嘉
蓝平
谢树明
谢涛
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Guangxi University for Nationalities
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/36—Organic compounds containing halogen

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Abstract

The invention discloses Sn/Sb-Mn-GAC particles, which are supported Sn/Sb-Mn-GAC particles prepared by loading modified granular activated carbon with Sn, Sb and Mn metal ions by adopting an immersion method. The method comprises the steps of constructing a multi-pole three-dimensional electrochemical reactor by taking supported Sn/Sb-Mn-GAC particles as particle electrodes, taking dimensionally stable anode DSA electrodes as anodes and taking titanium plates as cathodes, carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, and finally degrading 4-chlorophenol into carbon dioxide and water. The Sn/Sb-Mn-GAC particles are used for treating the 4-chlorophenol wastewater, and the removal rate of the 4-chlorophenol can reach more than 99 percent. Meanwhile, the particle preparation process is simple, the particles can be reused, the treatment cost of the 4-chlorophenol wastewater is greatly reduced, and the treatment efficiency of the 4-chlorophenol wastewater is improved.

Description

Sn/Sb-Mn-GAC particles and application thereof in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to preparation of Sn/Sb-Mn-GAC particles and application of the Sn/Sb-Mn-GAC particles in treatment of 4-chlorophenol wastewater through three-dimensional electrochemical reaction.
Background
With the rapid development of petrochemical, plastic, synthetic fiber and other industries, phenol-containing wastewater generated in production is discharged into the nature, which causes water pollution and simultaneously influences the growth and propagation of aquatic organisms. The phenol-containing waste water is a non-degradable toxic organic matter and is also a difficult point in environmental control, and the discharge of phenolic substances is strictly controlled at home and abroad.
The treatment of industrial wastewater containing phenols also becomes one of the hot research contents. At present, the waste water containing phenolic substances can be treated by an adsorption method generally, an adsorbent usually adopts activated carbon, but the treatment by the adsorption method only realizes the phase transfer of the phenolic substances and cannot carry out advanced and green treatment on toxic and harmful substances. The electrochemical oxidation is one of advanced oxidation technologies, has the advantages of strong oxidizability, high reaction rate, wide adaptability, no secondary pollution, simple treatment equipment, easy operation and control of electrolysis conditions and the like, and becomes one of research hotspots for treating the non-degradable toxic and harmful wastewater. Pongjie et al have investigated the effects of different factors on phenol treatment by treating phenol wastewater with an electrodialysis method using an ion exchange membrane. Experimental results show that the method has good treatment effect on the phenol wastewater, the energy consumption for treating the wastewater is low, and the operation process is convenient. ZUCHENGWU uses beta-PbO2The anode researches the oxidative degradation process of phenol, inspects the influence of initial pH value, current density and temperature on the degradation of phenol in the research process, conjectures the degradation path of phenol, and establishes a mathematical model of the oxidative degradation of phenol and benzoquinone. Royal bin et al used a self-made novel composite porous electrode-expanded graphite-based carbon/carbon composite electrode (EGC electrode) to perform electrochemical oxidative degradation on phenol, and discussed the degradation process conditions of phenol. The electro-Fenton method is a method combining an electrochemical method and a Fenton reagent method, and the basic principle of the electro-Fenton method is to ensure that O is electrolyzed in an acid solution2Reduction at the cathode to form H2O2Generation of H2O2Rapidly react with Fe2+Reaction to generate OH and Fe3+OH has high oxidation potential and has a potential value of 2.8V, and the strong oxidation capacity of OH can be used for oxidizing and degrading organic pollutants which are difficult to degrade into organic matters which are oxidized into small molecules or completely degraded into CO2And H2O; while Fe3+Can be reduced to Fe at the cathode2+Thereby forming a cycle for the oxidation reaction. The essence of the electro-Fenton method is that Fe is continuously generated by an electrochemical method2+And H2O2Forming a cycle. The electro-Fenton method is widely applied to experimental research on treatment of refractory wastewater containing phenols, organic acids, pesticides, organic synthetic dyes, personal care products and the like as a novel electrochemical treatment method. Baiwe et al treated phenol-containing wastewater by an electro-Fenton method, and the best reaction conditions for treating phenol simulation wastewater by the electro-Fenton method are obtained through experimental analysis: controlling pH value at 2, electrolytic voltage at 10V, reaction time at 60min, Na2SO4The concentration is 30g/L, the initial concentration of phenol is 150mg/L, and the removal rate of phenol treatment under the condition can reach 82%. The duyansheng, etc. uses the electricity-Fenton method to treat dinitrodiazophenol waste water. The experimental result shows that the best treatment condition of the dinitrodiazophenol wastewater is as follows: the electrolysis time is 3.5H, the pH value is 4, and the direct current voltage is 12V, H2O2The dosage of the dinitrodiazophenol is 10mL/L, under the treatment condition, the COD removal rate of the dinitrodiazophenol wastewater can reach 97.24 percent, and the chroma removal rate can reach 93.75 percent.
At present, phenol-containing industrial wastewater is mainly treated by an adsorption method, and activated carbon has a developed internal pore structure, large surface area, good chemical stability and strong acid and strong alkali resistance. Can withstand water immersion, high temperature and high pressure, and is a more common adsorbent. The Activated Carbon includes powdered Activated Carbon (GAC) and Granular Activated Carbon (GAC). The powdered activated carbon is easy to prepare, low in price and strong in adsorption capacity, but the powdered activated carbon is not easy to regenerate and poor in reusability. Compared with powdered activated carbon, the granular activated carbon is expensive, but can be regenerated and reused, and is a common material in water treatment.
Disclosure of Invention
The invention provides a preparation method of Sn/Sb-Mn-GAC particles and application of the Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, aiming at solving the problems of high removal difficulty, limited removal rate, high removal cost, complex operation and the like in the traditional treatment method of phenol-containing industrial wastewater in the prior art.
In order to achieve the above object of the present invention, the technical means of the present invention is as follows
The Sn/Sb-Mn-GAC particles are supported Sn/Sb-Mn-GAC particles prepared by loading modified granular activated carbon with Sn, Sb and Mn metal ions by adopting an immersion method.
As a further improvement of the technical scheme, the preparation method of the supported Sn/Sb-Mn-GAC particle comprises the following specific steps: firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in an organic alcohol solvent to obtain a mixed solution, soaking the GAC in the mixed solution, shaking for more than 2 hours by a shaking table at 200r/min to obtain a crude product of the load type Sn/Sb-Mn-GAC particles, drying, and roasting at the temperature of 300 ℃ and 500 ℃ to obtain the load type Sn/Sb-Mn-GAC particles.
As a further improvement of the technical scheme, in the preparation method of the Sn/Sb-Mn-GAC particles, the shaking table frequency is 150-.
As a further improvement of the technical solution, the Sn/Sb-Mn-GAC particles, SnCl, are described above4·5H2O、Mn(NO3)2、 SbCl3And GAC in a mass ratio of: 8-16: 1-5: 0.4-2: 60-80.
As a further improvement of the technical scheme, the Sn/Sb-Mn-GAC particles further comprise granular activated carbon pretreatment, wherein the granular activated carbon pretreatment is to boil and clean the granular activated carbon with a large amount of deionized water and dry the granular activated carbon.
As a further improvement of the technical scheme, in the preparation method of the Sn/Sb-Mn-GAC particles, the drying temperature is 100-110 ℃.
The Sn/Sb-Mn-GAC particle is applied to the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, a load type Sn/Sb-Mn-GAC particle is used as a particle electrode, a dimensionally stable anode DSA electrode is used as an anode, a titanium plate is used as a cathode, a multi-pole three-dimensional electrochemical reactor is constructed, the three-dimensional electrochemical reaction is carried out under the electrochemical oxidation action, and the 4-chlorophenol is finally degraded into carbon dioxide and water.
As a further improvement of the technical solution,the Sn/Sb-Mn-GAC particles are applied to the treatment of 4-chlorophenol wastewater through three-dimensional electrochemical reaction, and Na is used as electrolyte in the three-dimensional electrochemical reaction2SO4、NaCl、K2SO4And KCl.
As a further improvement of the technical scheme, the Sn/Sb-Mn-GAC particles are applied to the treatment of 4-chlorophenol wastewater through a three-dimensional electrochemical reaction, wherein in the three-dimensional electrochemical reaction, the concentration of the 4-chlorophenol wastewater is 100-500mg/L, the volume of simulated wastewater is 200-300mL, the concentration of an electrolyte is 2-4g/L, the plate interval between a cathode and an anode is 2-4cm, the reaction current is 1-2A, and the adding amount of particle electrodes is 10-20 g. As a further improvement of the technical scheme, the Sn/Sb-Mn-GAC particles are applied to the treatment of the 4-chlorophenol wastewater through three-dimensional electrochemical reaction, and the temperature of the three-dimensional electrochemical reaction is 40-60 ℃.
As a further improvement of the technical scheme, the Sn/Sb-Mn-GAC particles are applied to the treatment of 4-chlorophenol wastewater through three-dimensional electrochemical reaction, wherein in the three-dimensional electrochemical reaction, 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals, and is finally degraded into carbon dioxide and water; one or more than two of intermediate products of benzoquinone, 4-chlorocatechol, hydroquinone, fumaric acid and oxalic acid containing hydroxyl free radicals.
As a further improvement of the technical scheme, the Sn/Sb-Mn-GAC particles are applied to the treatment of the 4-chlorophenol wastewater through the three-dimensional electrochemical reaction, and the removal rate of the 4-chlorophenol in the 4-chlorophenol wastewater reaches more than 99%.
The invention has the following beneficial effects:
the Sn/Sb-Mn-GAC particles are prepared by adopting an immersion method, and compared with other preparation methods, the immersion method has the advantage of simple operation. Meanwhile, the granular activated carbon is used as a carrier of the particle electrode, so that the particle electrode has a better adsorption effect than particle electrodes of other carriers. The method is applied to a three-dimensional electrochemical reactor, greatly increases the area of a working electrode, improves the current efficiency, and has the advantages of more thorough degradation of 4-chlorophenol, no secondary pollution and the like compared with the degradation of 4-chlorophenol by other methods. Simultaneously, doping Mn in Sn-Sb is beneficial to changing SnO2The oxygen vacancy concentration in the crystal lattice improves the catalytic oxidation performance of the particle electrode, thereby greatly improving the degradation efficiency of the 4-chlorophenol.
Drawings
FIG. 1 is a scanning electron micrograph of Sn/Sb-Mn-GAC particles.
FIG. 2 is an EDS chart of surface elemental analysis of Sn/Sb-Mn-GAC particles.
FIG. 3 is an XRD pattern of Sn/Sb-Mn-GAC particle electrode
FIG. 4 is an oxygen evolution polarization curve of a Sn/Sb-Mn-GAC particle electrode
FIG. 5 is a cyclic voltammogram of a Sn/Sb-Mn-GAC particle electrode
FIG. 6 is a liquid chromatogram of 4-chlorophenol degradation process
In fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5, 4-Chlorophthalic acid
Detailed Description
Preparation of Sn/Sb-Mn-GAC particles example 1
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 8: 1: 0.4: 60 SnCl is weighed in turn4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in organic alcohol solvent to obtain mixed solution, soaking GAC in the mixed solution, shaking for 2 hours by a shaking table at 150r/min to obtain crude supported Sn/Sb-Mn-GAC particles, drying, and roasting at 300 ℃ to obtain the supported Sn/Sb-Mn-GAC particles.
Preparation of Sn/Sb-Mn-GAC particles example 2
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 10: 2: 1: 65 SnCl is weighed in turn4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in organic alcohol solvent to obtain mixed solution, soaking GAC in the mixed solution, shaking for 4 hours by a shaking table at 160r/min to obtain crude supported Sn/Sb-Mn-GAC particles, drying, and roasting at 350 ℃ to obtain the supported Sn/Sb-Mn-GAC particles.
Preparation of Sn/Sb-Mn-GAC particles example 3
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 12: 3: 1.5: 70 sequentially weighing SnCl4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in organic alcohol solvent to obtain mixed solution, soaking GAC in the mixed solution, shaking for 3 hours by a shaking table at 170r/min to obtain crude supported Sn/Sb-Mn-GAC particles, drying, and roasting at 400 ℃ to obtain the supported Sn/Sb-Mn-GAC particles.
Preparation of Sn/Sb-Mn-GAC particles example 4
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 14: 4: 42: 75 SnCl is weighed in turn4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in organic alcohol solvent to obtain mixed solution, soaking GAC in the mixed solution, shaking for 6 hours by a shaking table at 180r/min to obtain crude supported Sn/Sb-Mn-GAC particles, drying, and roasting at 450 ℃ to obtain the supported Sn/Sb-Mn-GAC particles.
Preparation of Sn/Sb-Mn-GAC particles example 5
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 16: 5: 2: 80 SnCl is weighed in turn4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in organic alcohol solvent to obtain mixed solution, soaking GAC in the mixed solution, shaking for 5 hours in a shaking table at 200r/min to obtain crude supported Sn/Sb-Mn-GAC particles, drying, and roasting at 500 ℃ to obtain the supported Sn/Sb-Mn-GAC particles.
Preparation of Sn/Sb-Mn-GAC particles example 1
(1) Pretreatment of granular activated carbon: boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying for later use.
(2) The weight ratio is as follows: 8-16: 1-5: 0.4-2: 60-80. Sequentially weighing SnCl4·5H2O、Mn(NO3)2、SbCl3And GAC.
(3) Firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in an organic alcohol solvent to obtain a mixed solution, soaking the GAC in the mixed solution, shaking for more than 2 hours by a shaking table at 200r/min to obtain a crude product of the load type Sn/Sb-Mn-GAC particles, drying, and roasting at the temperature of 300 ℃ and 500 ℃ to obtain the load type Sn/Sb-Mn-GAC particles.
Determination of physicochemical Properties of Supported Sn/Sb-Mn-GAC particles prepared in example 1
Analyzing the surface morphology and the structure of the particle electrode:
(1) analysis by scanning Electron microscope
The surface morphology of the activated carbon was analyzed using a field emission scanning electron microscope (SUPRA 55 Sapphire, Calitz, Germany), and the elemental composition on the modified activated carbon was analyzed using an OXORD X-MaxN51-XMX1004 energy spectrometer configured with this scanning electron microscope.
(2) X-ray diffraction analysis
The activated carbon was analyzed using an X-ray diffractometer (X' Pert PRO, Panalytical, Pa., Netherlands) under the following test conditions: copper target
Figure BDA0001469775510000051
Step size is 0.026 deg., scanning range is 5-80 deg., residence time of each step is 20.4s, voltage is 40V, and current is 40 mA.
Testing electrochemical performance of the particle electrode:
the electrochemical performance test of the supported particle electrode mainly provides a theoretical basis for an electrocatalytic oxidation mechanism, and the electrochemical performance is generally tested by using a three-electrode system. The electrochemical performance of the particle electrode is tested by adopting Chenghua CHI660E electrochemical workstation, and the electrochemical performance is tested by taking a self-made carbon paste electrode as a working electrode, a saturated calomel electrode as a reference electrode and a platinum electrode as an auxiliary electrode. The manufacturing method of the carbon paste electrode comprises the following steps: taking a proper amount of particle electrodes, grinding into powder, and mixing the powder with the particle electrodes: adding a certain amount of conductive carbon black in an amount of 8:1, uniformly mixing the particle electrode powder and the conductive carbon black, adding liquid paraffin to prepare paste, and filling the paste into a carbon paste electrode. In the range of 1-1.5V, at a sweep rate of 20mV/s, respectively at 0.15mol/LNa2SO4And 0.15mol/LNa2SO4In +0.5 g/L4-chlorophenol solution, its linear voltammetry working curve and cyclic voltammetry curve were measured.
The test shows that:
the scanning electron microscope image of the Sn/Sb-Mn-GAC particles is shown in figure 1, and figure 1 shows that the particle size of the Sn/Sb-Mn-GAC surface is small, the particle size of the activated carbon surface is fine and uniform, the dispersibility is good, and the specific surface area of the particle electrode can be effectively increased when the activated carbon surface is used as a three-dimensional electrode, so that the contact area between the particle electrode surface and organic pollutants is increased, and the electro-oxidation reaction efficiency is improved.
EDS (elemental analysis) chart of Sn/Sb-Mn-GAC particle surface is shown in figure 2, and figure 2 shows that the corresponding Sn/Sb-Mn metal oxide is successfully loaded on GAC.
The XRD pattern of the Sn/Sb-Mn-GAC particle electrode is shown in figure 3, and figure 3 shows that the Sn/Sb-Mn-GAC only has a Sn element characteristic diffraction peak at a 2 theta angle of 26.7 degrees, and no Mn element and Sb element characteristic diffraction peaks are found, but the existence of manganese and antimony elements is detected by energy spectrum analysis, which indicates that the manganese-containing oxide and the antimony-containing oxide are distributed on the surface of the GAC in an amorphous form.
The oxygen evolution polarization curve of the Sn/Sb-Mn-GAC particle electrode is shown in FIG. 4, and FIG. 4 shows that the current of the Sn/Sb-Mn-GAC particle electrode in the oxygen evolution area is between 1.6V and 1.8V. The oxygen evolution potential is an important factor influencing the electrochemical degradation efficiency of organic pollutants, when the electrode oxygen evolution potential is low, an electrochemical reaction is carried out, and an oxygen evolution side reaction is easy to occur, so that the removal efficiency of the organic pollutants is reduced, therefore, when the activated carbon is loaded, loaded activated carbon particles with high oxygen evolution potential are expected to be obtained, so that more electrons participate in the removal of the organic pollutants, and the current efficiency of the electrochemical reaction is improved.
The cyclic voltammogram of the Sn/Sb-Mn-GAC particle electrode is shown in FIG. 5, and FIG. 5 shows that the Sn/Sb-Mn-GAC has an oxidation peak before an oxygen evolution potential, which indicates that the 4-chlorophenol has direct catalytic oxidation reaction when the supported activated carbon is the particle electrode. In the direct oxidation process, contaminants are first adsorbed on the electrode surface and then degraded by electron transfer.
Further, the supported Sn/Sb-Mn-GAC particles prepared in examples 2 to 5 were selected and subjected to the same tests as the supported Sn/Sb-Mn-GAC particles prepared in example 1, and the results obtained by the tests of all the examples were highly consistent with the tests corresponding to the supported Sn/Sb-Mn-GAC particles prepared in example 1, indicating that the prepared product was excellent in reproducibility.
Application of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
Application example 1 of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
The application of the Sn/Sb-Mn-GAC particles in the three-dimensional electrochemical reaction treatment of the 4-chlorophenol wastewater: preparation of Sn/Sb-Mn-GAC particles the supported Sn/Sb-Mn-GAC particles prepared in example 1 were used as particle electrodes, dimensionally stable anode DSA electrodes as anodes, titanium plates as cathodes, and Na2SO4A multi-pole three-dimensional electrochemical reactor is constructed for electrolyte, the concentration of the 4-chlorophenol wastewater is 100mg/L, the volume of the simulated wastewater is 200mL, the concentration of the electrolyte is 2g/L, the plate interval between a cathode and an anode is 2cm, the reaction current is 1A, and the particle electrode is arrangedThe amount of the addition was 10 g. Carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, wherein the temperature of the three-dimensional electrochemical reaction is 40 ℃, and degrading the 4-chlorophenol into an intermediate product containing hydroxyl free radicals, and finally degrading into carbon dioxide and water.
When the electrochemical reaction is half-way completed, performing ideal chromatographic detection on the reaction solution to obtain a liquid chromatogram in the 4-chlorophenol degradation process shown in fig. 6, wherein in fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5.4-chlorophthalic acid, FIG. 6 shows that the intermediates such as oxalic acid, fumaric acid, hydroquinone, p-benzoquinone, 4-chlorophthalic acid, etc. are mainly produced during the degradation of 4-chlorophenol.
And (3) after the electrochemical reaction is finished, analyzing the concentration of the 4-chlorophenol in the system by adopting a liquid chromatography, calculating the removal rate of the 4-chlorophenol, and observing the influence of different load particle electrodes on the 4-chlorophenol simulation wastewater treatment effect by taking the removal rate of the 4-chlorophenol, electric energy and current efficiency as indexes. The 4-chlorophenol removal rate was calculated as follows.
4-chlorophenol removal rate y (%):
Figure BDA0001469775510000061
in the formula: c0Is the initial concentration (mg/L) of 4-chlorophenol, CtThe concentration of 4-chlorophenol at time t (mg/L).
Through detection, the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater in the embodiment reaches 99.5%.
Application example 2 of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
The application of the Sn/Sb-Mn-GAC particles in the three-dimensional electrochemical reaction treatment of the 4-chlorophenol wastewater: the supported Sn/Sb-Mn-GAC particles prepared in the preparation example 2 of Sn/Sb-Mn-GAC particles are used as particle electrodes, dimensionally stable anode DSA electrodes are used as anodes, titanium plates are used as cathodes, NaCl is used as electrolyte, a multi-pole three-dimensional electrochemical reactor is constructed, the concentration of 4-chlorophenol wastewater is 200mg/L, the volume of simulated wastewater is 225mL, the concentration of the electrolyte is 2.5g/L, the plate distance between the cathode and the anode is 2.5cm, the reaction current is 1.25A, and the adding amount of the particle electrodes is 12 g. Carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, wherein the temperature of the three-dimensional electrochemical reaction is 45 ℃, and the 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals and is finally degraded into carbon dioxide and water.
When the electrochemical reaction is half-way completed, performing ideal chromatographic detection on the reaction solution to obtain a liquid chromatogram in the 4-chlorophenol degradation process shown in fig. 6, wherein in fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5.4-chlorophthalic acid, FIG. 6 shows that the intermediates such as oxalic acid, fumaric acid, hydroquinone, p-benzoquinone, 4-chlorophthalic acid, etc. are mainly produced during the degradation of 4-chlorophenol.
And (3) after the electrochemical reaction is finished, analyzing the concentration of the 4-chlorophenol in the system by adopting a liquid chromatography, calculating the removal rate of the 4-chlorophenol, and observing the influence of different load particle electrodes on the 4-chlorophenol simulation wastewater treatment effect by taking the removal rate of the 4-chlorophenol, electric energy and current efficiency as indexes. The 4-chlorophenol removal rate was calculated as follows.
4-chlorophenol removal rate y (%):
Figure BDA0001469775510000071
in the formula: c0Is the initial concentration (mg/L) of 4-chlorophenol, CtThe concentration of 4-chlorophenol at time t (mg/L).
Through detection, the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater in the embodiment reaches over 99.8%.
Application example 3 of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
The application of the Sn/Sb-Mn-GAC particles in the three-dimensional electrochemical reaction treatment of the 4-chlorophenol wastewater: the supported Sn/Sb-Mn-GAC particles prepared in the preparation example 3 of Sn/Sb-Mn-GAC particles were used as particle electrodes, dimensionally stable anode DSA electrodes were used as anodes, titanium plates were used as cathodes, and K was used as a cathode2SO4Constructing a multi-pole three-dimensional electrochemical reactor for electrolyte, wherein the concentration of the 4-chlorophenol wastewater is 300mg/L, the volume of the simulated wastewater is 250mL, the concentration of the electrolyte is 3g/L, and the concentration of the cathode and the anode areThe plate gap was 3cm, the reaction current was 1.5A, and the amount of particle electrode added was 15 g. Carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, wherein the temperature of the three-dimensional electrochemical reaction is 50 ℃, and the 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals and is finally degraded into carbon dioxide and water.
When the electrochemical reaction is half-way completed, performing ideal chromatographic detection on the reaction solution to obtain a liquid chromatogram in the 4-chlorophenol degradation process shown in fig. 6, wherein in fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5.4-chlorophthalic acid, FIG. 6 shows that the intermediates such as oxalic acid, fumaric acid, hydroquinone, p-benzoquinone, 4-chlorophthalic acid, etc. are mainly produced during the degradation of 4-chlorophenol.
And (3) after the electrochemical reaction is finished, analyzing the concentration of the 4-chlorophenol in the system by adopting a liquid chromatography, calculating the removal rate of the 4-chlorophenol, and observing the influence of different load particle electrodes on the 4-chlorophenol simulation wastewater treatment effect by taking the removal rate of the 4-chlorophenol, electric energy and current efficiency as indexes. The 4-chlorophenol removal rate was calculated as follows.
4-chlorophenol removal rate y (%):
Figure BDA0001469775510000081
in the formula: c0Is the initial concentration (mg/L) of 4-chlorophenol, CtThe concentration of 4-chlorophenol at time t (mg/L).
Through detection, the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater in the embodiment reaches 99.6%.
Application example 4 of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
The application of the Sn/Sb-Mn-GAC particles in the three-dimensional electrochemical reaction treatment of the 4-chlorophenol wastewater: the supported Sn/Sb-Mn-GAC particles prepared in the preparation example 4 of Sn/Sb-Mn-GAC particles are used as particle electrodes, dimensionally stable anode DSA electrodes are used as anodes, titanium plates are used as cathodes, KCl is used as electrolyte, a bipolar three-dimensional electrochemical reactor is constructed, the concentration of 4-chlorophenol wastewater is 400mg/L, the volume of simulated wastewater is 275mL, the concentration of the electrolyte is 3.5g/L, the plate distance between the cathodes and the anodes is 3.5cm, the reaction current is 1.75A, and the adding amount of the particle electrodes is 18 g. Carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, wherein the temperature of the three-dimensional electrochemical reaction is 55 ℃, and the 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals and is finally degraded into carbon dioxide and water.
When the electrochemical reaction is half-way completed, performing ideal chromatographic detection on the reaction solution to obtain a liquid chromatogram in the 4-chlorophenol degradation process shown in fig. 6, wherein in fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5.4-chlorophthalic acid, FIG. 6 shows that the intermediates such as oxalic acid, fumaric acid, hydroquinone, p-benzoquinone, 4-chlorophthalic acid, etc. are mainly produced during the degradation of 4-chlorophenol.
And (3) after the electrochemical reaction is finished, analyzing the concentration of the 4-chlorophenol in the system by adopting a liquid chromatography, calculating the removal rate of the 4-chlorophenol, and observing the influence of different load particle electrodes on the 4-chlorophenol simulation wastewater treatment effect by taking the removal rate of the 4-chlorophenol, electric energy and current efficiency as indexes. The 4-chlorophenol removal rate was calculated as follows.
4-chlorophenol removal rate y (%):
Figure BDA0001469775510000082
in the formula: c0Is the initial concentration (mg/L) of 4-chlorophenol, CtThe concentration of 4-chlorophenol at time t (mg/L).
Through detection, the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater in the embodiment reaches 99.8%.
Application example 5 of Sn/Sb-Mn-GAC particles in three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater
The application of the Sn/Sb-Mn-GAC particles in the three-dimensional electrochemical reaction treatment of the 4-chlorophenol wastewater: preparation of Sn/Sb-Mn-GAC particles the supported Sn/Sb-Mn-GAC particles prepared in example 5 were used as particle electrodes, dimensionally stable anode DSA electrodes as anodes, titanium plates as cathodes, and Na2SO is used as electrolyte, a bipolar three-dimensional electrochemical reactor is constructed, the concentration of the 4-chlorophenol wastewater is 500mg/L, the volume of the simulated wastewater is 300mL, and electrolysis is carried outThe mass concentration is 4g/L, the plate distance between the cathode and the anode is 4cm, the reaction current is 2A, and the addition amount of the particle electrode is 20 g. Carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, wherein the temperature of the three-dimensional electrochemical reaction is 60 ℃, and the 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals and is finally degraded into carbon dioxide and water.
When the electrochemical reaction is half-way completed, performing ideal chromatographic detection on the reaction solution to obtain a liquid chromatogram in the 4-chlorophenol degradation process shown in fig. 6, wherein in fig. 6: 1. oxalic acid; 2. fumaric acid; 3. hydroquinone; 4. p-benzoquinone; 5.4-chlorophthalic acid, FIG. 6 shows that the intermediates such as oxalic acid, fumaric acid, hydroquinone, p-benzoquinone, 4-chlorophthalic acid, etc. are mainly produced during the degradation of 4-chlorophenol.
And (3) after the electrochemical reaction is finished, analyzing the concentration of the 4-chlorophenol in the system by adopting a liquid chromatography, calculating the removal rate of the 4-chlorophenol, and observing the influence of different load particle electrodes on the 4-chlorophenol simulation wastewater treatment effect by taking the removal rate of the 4-chlorophenol, electric energy and current efficiency as indexes. The 4-chlorophenol removal rate was calculated as follows.
4-chlorophenol removal rate y (%):
Figure BDA0001469775510000091
in the formula: c0Is the initial concentration (mg/L) of 4-chlorophenol, CtThe concentration of 4-chlorophenol at time t (mg/L).
Through detection, the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater in the embodiment reaches 99.6%.

Claims (7)

  1. Sn/Sb-Mn-GAC particles, characterized in that: the Sn/Sb-Mn-GAC particles are load type Sn/Sb-Mn-GAC particles prepared by loading modified granular activated carbon with Sn, Sb and Mn metal ions by adopting an immersion method;
    the method also comprises the pretreatment of granular activated carbon, wherein the pretreatment of the granular activated carbon comprises the steps of boiling and cleaning the granular activated carbon with a large amount of deionized water, and drying; the preparation method of the load type Sn/Sb-Mn-GAC particle comprises the specific stepsThe method comprises the following steps: firstly SnCl4·5H2O、Mn(NO3)2、SbCl3Dissolving in an organic alcohol solvent to obtain a mixed solution, soaking the GAC in the mixed solution, shaking for more than 2 hours by a shaking table at 200r/min to obtain a crude product of the load type Sn/Sb-Mn-GAC particles, drying, and roasting at the temperature of 300 ℃ and 500 ℃ to obtain the load type Sn/Sb-Mn-GAC particles;
    the Sn element in the Sn/Sb-Mn-GAC particles is distributed on the surface of the GAC in a crystal form, and the other two elements Sb and Mn are distributed on the surface of the GAC in an amorphous form; the current of the Sn/Sb-Mn-GAC particle electrode in an oxygen evolution area is between 1.6V and 1.8V;
    SnCl4·5H2O、Mn(NO3)2、SbCl3and GAC mass ratio: 8-16: 1-5: 0.4-2: 60-80.
  2. 2. Use of the Sn/Sb-Mn-GAC particles of claim 1 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, wherein: the method comprises the steps of constructing a multi-pole three-dimensional electrochemical reactor by taking supported Sn/Sb-Mn-GAC particles as particle electrodes, taking dimensionally stable anode DSA electrodes as anodes and taking titanium plates as cathodes, carrying out three-dimensional electrochemical reaction under the action of electrochemical oxidation, and finally degrading 4-chlorophenol into carbon dioxide and water.
  3. 3. The use of the Sn/Sb-Mn-GAC particles according to claim 2 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, wherein: the electrolyte adopted by the three-dimensional electrochemical reaction is Na2SO4、NaCl、K2SO4And KCl.
  4. 4. The use of the Sn/Sb-Mn-GAC particles according to claim 2 or 3 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, characterized in that: in the three-dimensional electrochemical reaction, the concentration of the 4-chlorophenol wastewater is 500mg/L, the volume of the simulated wastewater is 200 mL-300 mL, the concentration of the electrolyte is 2-4g/L, the plate interval between the cathode and the anode is 2-4cm, the reaction current is 1-2A, and the addition amount of the particle electrode is 10-20 g.
  5. 5. The use of the Sn/Sb-Mn-GAC particles according to claim 4 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, wherein: the temperature of the three-dimensional electrochemical reaction is 40-60 ℃.
  6. 6. The use of the Sn/Sb-Mn-GAC particles according to claim 2 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, wherein: in the three-dimensional electrochemical reaction, 4-chlorophenol is firstly degraded into an intermediate product containing hydroxyl free radicals, and is finally degraded into carbon dioxide and water; the intermediate product containing hydroxyl free radical is one or the mixture of more than two of p-benzoquinone, 4-chlorocatechol, hydroquinone, fumaric acid and oxalic acid.
  7. 7. The use of the Sn/Sb-Mn-GAC particles according to claim 2 in the three-dimensional electrochemical reaction treatment of 4-chlorophenol wastewater, wherein: the removal rate of 4-chlorophenol in the 4-chlorophenol wastewater reaches more than 99%.
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