CN115536183A - Based on DSA (MnO) X -Ti) cathode ozone/electrochemical coupling printing and dyeing wastewater treatment method of water treatment system - Google Patents

Based on DSA (MnO) X -Ti) cathode ozone/electrochemical coupling printing and dyeing wastewater treatment method of water treatment system Download PDF

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CN115536183A
CN115536183A CN202211340893.5A CN202211340893A CN115536183A CN 115536183 A CN115536183 A CN 115536183A CN 202211340893 A CN202211340893 A CN 202211340893A CN 115536183 A CN115536183 A CN 115536183A
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mnox
ozone
printing
cathode
dyeing wastewater
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韩卫清
于酉宁
魏卡佳
张�杰
朱晶晶
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

Abstract

The invention discloses a printing and dyeing wastewater treatment method of an ozone/electrochemical coupling water treatment system based on a DSA (MnOx-Ti) cathode, belonging to the technical fields of material chemistry, electrochemistry and ozone oxidation. Wherein the cathode material is MnOx-Ti, the cathode takes a metallic titanium sheet as a matrix, and MnCl is processed by a sol-gel method 2 Brushing on a metal titanium sheet, and putting the titanium sheet into a box-type resistance furnace to prepare the titanium alloy at 350-500 ℃; the processing method comprises the following steps: firstly, conveying printing and dyeing wastewater into an electrochemical reactor through a pump, introducing ozone, and performing ozone catalytic oxidation treatment; then the power supply is turned on to carry out electrocatalysis treatment. The invention provides a cathode material DSA (MnOx-Ti) of an ozone/electrochemical coupling water treatment system, which couples ozone catalytic oxidation treatment with an electrochemical technology,can realize the cooperative removal of conventional pollutants and organic halides in the dye wastewater, ensure the stable and standard-reaching quality of the effluent, and has wide application prospect.

Description

Based on DSA (MnO) X -Ti) cathode ozone/electrochemical coupling printing and dyeing wastewater treatment method of water treatment system
Technical Field
The invention belongs to the field of material chemistry and printing and dyeing wastewater treatment, and particularly relates to a printing and dyeing wastewater treatment method of an ozone/electrochemical coupling water treatment system based on a DSA (MnOx-Ti) cathode.
Background
The printing and dyeing wastewater has high COD and total nitrogen content, fixed biological toxicity and poor biodegradability, and is typical industrial wastewater difficult to treat. The printing and dyeing wastewater contains various refractory organic matters such as dye, reagent, fallen textile fabrics, printing and dyeing auxiliary agent and the like, and has complex components and difficult treatment. The azo dye wastewater has high chemical oxygen demand, high total nitrogen content, poor biodegradability, high chromaticity and violent water quality change, and may also contain heavy metal ions such as zinc, copper and the like, cyanide and the like. Common technologies for treating printing and dyeing wastewater include biomass adsorption, membrane technology, advanced oxidation technology, anaerobic-aerobic combined biological treatment technology and the like. The membrane module is easy to be polluted and blocked when the membrane technology is higher in operation cost. Although the anaerobic-aerobic combined process has a good decolorizing effect, the printing and dyeing wastewater has poor biodegradability and large water quality change, and needs to be subjected to severe pretreatment before treatment. The advanced oxidation technology can realize the complete degradation of dye molecules and organic matters, has the advantages of high reaction rate, good decolorization effect, no secondary pollution and the like, and has wide research and application in the treatment of printing and dyeing wastewater.
The advanced oxidation technology can remove dye molecules in the printing and dyeing wastewater through high-efficiency oxidation, complete degradation of organic matters is realized, and excellent decolorization degradation capability is shown; however, the following problems still remain in the degradation of printing and dyeing wastewater, and it is highly important.
1. The method can effectively remove the molecules of the dye which is difficult to degrade, but has strict requirements on pH, catalyst and oxidant, and the catalyst is difficult to recover and is easy to cause secondary pollution.
2. How to more efficiently excite strong oxidizing free radicals such as OH, SO and the like and efficiently oxidize and degrade dye molecules through free radical reaction.
S, developing an ozone oxidation catalyst, and developing a dye adsorbent and a catalyst by using a waste runner so as to ensure that the development concept of environmental protection is better met.
Disclosure of Invention
The invention aims to provide a printing and dyeing wastewater treatment method of an ozone/electrochemical coupling water treatment system based on a DSA (MnOx-Ti) cathode, which utilizes a cathode material DSA (MnOx-Ti) and couples ozone catalytic oxidation treatment with electrochemical treatment, can realize the synergistic removal of conventional pollutants and organic halides in dye wastewater, and ensures the safe discharge of the dye wastewater.
The technical scheme of the invention is as follows:
the invention provides a printing and dyeing wastewater treatment method of an ozone/electrochemical coupling water treatment system based on a DSA (MnOx-Ti) cathode, which comprises the following steps:
s1, firstly, conveying printing and dyeing wastewater into an electrochemical reactor through a pump;
s2, introducing ozone into the printing and dyeing wastewater to perform ozone catalytic oxidation treatment;
s3, carrying out electrocatalysis treatment on the printing and dyeing wastewater treated in the step S2; wherein the cathode material is MnOx-Ti, the cathode takes a metallic titanium sheet as a matrix, and MnCl is processed by a sol-gel method 4 Brushing a metal titanium sheet, and putting the titanium sheet into a box-type resistance furnace at 350-500 ℃ to obtain the titanium sheet; wherein MnOx is MnO 2 And Mn 3 O 4 A mixture of (a).
According to the method, a cathode material DSA (MnOx-Ti) of the ozone/electrochemical coupling water treatment system is used as a cathode and an ozone catalyst, and firstly, the dye wastewater is subjected to catalytic oxidation treatment by ozone, so that the chroma and COD of the dye wastewater are reduced; and then, carrying out electrocatalysis reduction dehalogenation treatment to further remove halogenated organic matters in the wastewater and organic halogenated byproducts generated in the ozone catalytic oxidation process, finally realizing the cooperative removal of conventional pollutants and organic halogenated matters in the dye wastewater, overcoming the defect that the existing ozone oxidation process is easy to generate high-toxicity halogenated byproducts, ensuring the safe discharge of the dye wastewater, and being suitable for the advanced treatment of high-salinity wastewater.
In some embodiments, in the MnOx-Ti electrode, the pore size of the base titanium sheet is 2 μm; the load capacity of MnOx-Ti on the substrate titanium sheet is 0.35-0.40mg/cm 2 。
In some embodiments, the MnOx-Ti electrode has a cathode material MnOx-Ti firing temperature of 350 to 500 deg.C, and most preferably 450 deg.C.
In some embodiments, the pH of the treated wastewater is adjusted to 1-3, and most preferably 2, prior to the catalytic ozonation treatment.
In some embodiments, O 3 The concentration is 30-35mg/L, the optimal concentration is 33mg/L, and the hydraulic retention time is 15-30min, the optimal concentration is 20min.
In some embodiments, the electrolyte is a sodium sulfate solution having a concentration of 50 to 60 mmol/L.
In some embodiments, the constant current is controlled to be 0.75-0.80A and the current density is controlled to be 15A/m 2 -20A/m 2 Most preferably 18A/m 2 。
In some embodiments, the cathode material is MnOx-Ti prepared by a method comprising:
s1, pretreatment of a titanium substrate: preparing a NaOH solution with the mass fraction of 40%, then putting the titanium substrate into the solution, cleaning for 60min at 80 ℃, preparing an oxalic acid solution with the mass fraction of 15%, and boiling the titanium substrate treated by the NaOH in the oxalic acid solution for 100min;
the preparation method of the S2 MnOx precursor comprises the following steps: electrode brush precursor preparation was prepared according to the classic h.b. beer patent: weighing 4g of MnCl 2 With 250ml of analytically pure isopropanol and 4ml of 37% pure hydrochloric acid. Then placing the precursor in a magnetic stirrer to stir for 24 hours to obtain a precursor of the MnOx electrode;
the preparation method of the S3 MnOx-Ti cathode material comprises the following steps:
(a) And (3) drying the pretreated titanium substrate by an oven, then placing the dried titanium substrate into a vacuum induction device, sealing and opening a circulating water vacuum pump, and pumping the device to a vacuum state (pumping to the state that a vacuum gauge pointer does not move). Then slowly rotating the test tube to enable the brush-coated precursor to flow into the three-neck flask until the liquid level is over the titanium substrate; opening the three-neck flask to release pressure, wherein the brush-coated precursor enters micropores of the titanium substrate, and taking out the titanium substrate to prepare for the next step;
(b) Besides the micropores, the surface of the titanium substrate needs to be coated with the precursor by brush coating. In order to ensure that the precursor can be uniformly dispersed on the surface of the titanium substrate, the coating must be slowly and repeatedly coated. After the brush coating is finished, drying the mixture in a drying oven at 105 ℃ for 10min to volatilize the solvent;
(c) And (3) putting the dried titanium substrate into a box-type resistance furnace at 450 ℃ to sinter for 15min in the air, wherein the heating rate is 5 ℃/min. After repeating the above 3 steps for 21 times, sintering in a box-type resistance furnace at 550 ℃ for 1h.
In the finally prepared MnOx-Ti cathode, the aperture of the matrix titanium sheet is 2 mu m; the load capacity of MnOx-Ti on the substrate titanium sheet is 0.35-0.40mg/cm 2 。
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. the method utilizes cathode material DSA (MnOx-Ti) to couple the catalytic oxidation treatment of ozone with the electrochemical technology, can efficiently remove aromatic pollutants in the dye wastewater, and overcomes the defect that the existing ozone oxidation process is easy to generate high-toxicity halogenated byproducts; 2. the method can realize the cooperative removal of conventional pollutants and organic halogenated pollutants in a high-salt environment, thereby ensuring that the effluent quality stably reaches the standard, and adding no catalyst on the basis of the advantages of the original traditional cathode; 3. the method has the advantages of simple process flow, mild reaction conditions and wide application prospect in the advanced treatment of high-salinity wastewater.
Drawings
FIG. 1 is a flow chart of an electrocatalysis-ozone coupling process.
Fig. 2 is a graph of TOC degradation rate as a function of HRT (hydraulic retention time).
FIG. 3 is a graph showing the change of COD removal rate with the calcination temperature.
FIG. 4 is a comparison graph of the colorimetric treatment effect of different reaction systems under the optimal operating conditions.
Detailed Description
The present invention is described in further detail below by way of specific examples.
The cathode material MnOx-Ti in the ozone/electrochemical coupling water treatment system is prepared by the method comprising the following steps:
s1, pretreatment of a titanium substrate: preparing a NaOH solution with the mass fraction of 40%, then putting the titanium substrate into the solution, cleaning for 60min at 80 ℃, preparing an oxalic acid solution with the mass fraction of 15%, and boiling the titanium substrate treated by the NaOH in the oxalic acid solution for 100min;
the preparation method of the S2 MnOx precursor comprises the following steps: electrode brush precursor preparation was prepared according to the classic h.b. beer patent: weighing 4g of MnCl 2 With 250ml of analytically pure isopropanol and 4ml of 37% pure hydrochloric acid. Then placing the precursor in a magnetic stirrer to stir for 24 hours to obtain a precursor of the MnOx electrode;
the preparation method of the S3 MnOx-Ti cathode material comprises the following steps:
(a) And (3) drying the pretreated titanium substrate by an oven, then placing the dried titanium substrate into a vacuum induction device, sealing and opening a circulating water vacuum pump, and pumping the device to a vacuum state (pumping to the state that a vacuum gauge pointer does not move). Then slowly rotating the test tube to enable the brush-coated precursor to flow into the three-neck flask until the liquid level is over the titanium substrate; then opening the three-neck flask to release pressure, wherein the brush-coating precursor can enter micropores of the titanium substrate, and taking out the titanium substrate to prepare for the next step;
(b) Besides the micropores, the surface of the titanium matrix needs to be coated with the precursor by brush coating. In order to ensure that the precursor can be uniformly dispersed on the surface of the titanium substrate, the coating must be slowly and repeatedly coated. After the brush coating is finished, drying the mixture in a drying oven at 105 ℃ for 10min to volatilize the solvent;
(c) And (3) putting the dried titanium substrate into a box-type resistance furnace at 450 ℃ to sinter for 15min in the air, wherein the heating rate is 5 ℃/min. After repeating the above 3 steps for 21 times, sintering in a box-type resistance furnace at 550 ℃ for 1h.
In the finally prepared MnOx-Ti cathode, the aperture of the matrix titanium sheet is 2 mu m; the load capacity of MnOx-Ti on the substrate titanium sheet is 0.35-0.40mg/cm 2 。
Example 1
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L(ii) a Adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: adopting MnOx-Ti electrode as cathode and ruthenium dioxide (RnO) 2 ) The electrode was the anode and HRT (hydraulic retention time) was 15min.
Example 2
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: adopting MnOx-Ti electrode as cathode and ruthenium dioxide (RnO) 2 ) The electrode was the anode and HRT (hydraulic retention time) was 20min.
Example 3
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: adopting MnOx-Ti electrode as cathode and ruthenium dioxide (RnO) 2 ) The electrode was the anode and HRT (hydraulic retention time) was 25min.
Example 4
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: adopting MnOx-Ti electrode as cathode and ruthenium dioxide (RnO) 2 ) The electrode was the anode and HRT (hydraulic retention time) was 30min.
Example 5
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: a MnOx-Ti electrode is used as a cathode, a ruthenium dioxide (RnO 2) electrode is used as an anode, and the HRT (hydraulic retention time) is 40min.
FIG. 2 is a graph showing the variation of TOC degradation rate with HRT (hydraulic retention time) in examples 1 to 5 of the present invention, and it can be seen from FIG. 2 that when the hydraulic retention time is 15min, the TOC degradation rate after the operation of the reaction system is stabilized is 55.8%, and when the hydraulic retention time is 20min, the TOC degradation rate after the operation of the reaction system is stabilized is 62.4%, which indicates that when HRT =15min, the reaction system does not exert its maximum effect, and HRT is continuously increased, and it is found that the treatment effect is not significantly improved, and when HRT =40min, the TOC degradation rate is 66.5%, which is only 3.9% higher than HRT =20min, and considering that the extension of HRT increases the external electric energy of the electrochemical catalytic reaction system, and at the same time, the increase of HRT wastes O that cannot be dissolved into the liquid phase due to the saturation state 3 Since the processing cost increases, HRT =20min is selected as the optimum HRT. The TOC degradation rate is about 60%.
Example 6
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: a MnOx-Ti electrode is used as a cathode (roasting temperature is 350 ℃), a ruthenium dioxide (RnO 2) electrode is used as an anode, and HRT (hydraulic retention time) is 40min.
Example 7
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: a MnOx-Ti electrode is used as a cathode (the roasting temperature is 400 ℃), a ruthenium dioxide (RnO 2) electrode is used as an anode, and the HRT (hydraulic retention time) is 40min.
Example 8
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: the MnOx-Ti electrode is used as a cathode (the roasting temperature is 450 ℃), the ruthenium dioxide (RnO 2) electrode is used as an anode, and the HRT (hydraulic retention time) is 40min.
Example 9
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: the MnOx-Ti electrode is used as a cathode (the roasting temperature is 500 ℃), the ruthenium dioxide (RnO 2) electrode is used as an anode, and the HRT (hydraulic retention time) is 40min.
FIG. 3 is a graph showing the change of COD removal rate with the firing temperature in examples 6 to 9 of the present invention, and it can be seen from FIG. 3 that the higher the firing temperature is, the higher the COD removal rate of the produced MnOx-Ti cathode for the ozone oxidation coupled electrochemical treatment of printing and dyeing wastewater is. The curves of the roasting temperature of 450 ℃ and the roasting temperature of 500 ℃ are basically similar, and the roasting temperature of 450 ℃ is greatly improved compared with the roasting temperature of 400 ℃ and the roasting temperature of 350 ℃, which shows that the MnOx-Ti cathode has the strongest performance when the roasting temperature is 450 ℃.
Example 10
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: a Ti electrode is used as a cathode, a ruthenium dioxide (RnO 2) electrode is used as an anode, and HRT (hydraulic retention time) is 10min.
Example 11
A printing and dyeing wastewater treatment method based on ozone oxidation coupled electrochemistry comprises the following steps:
500ml of printing and dyeing wastewater is taken from a dye wastewater treatment plant in a certain chemical industry park, the TOC concentration of the wastewater is 20mg/L, and the pH value is 8.
At normal temperature, ozone is introduced into the original printing and dyeing wastewater through an aeration head, and the concentration of the ozone is 34mg/L; adjusting the pH value of the treated wastewater to 2 by using concentrated sulfuric acid; and then carrying out electrochemical treatment: an electrode MnOx-Ti is used as a cathode, a ruthenium dioxide (RnO 2) electrode is used as an anode, and the HRT (hydraulic retention time) is 10min.
Fig. 4 is a comparison of the chromaticity treatment effects of different reaction systems under the optimal operation conditions in examples 10 to 11 of the present invention, and it can be seen from fig. 4 that the electrocatalysis-ozone coupling and the electrocatalysis-ozone coupling both of which take MnOx-Ti as a cathode have good effects on the chromaticity removal of printing and dyeing wastewater, and after the reaction system operates for 5min, the chromaticity of effluent is close to 0 degree, compared with the electrochemical-catalytic oxidation reaction system which has a weak capability of removing chromaticity, and after the reaction system operates for 10min, the chromaticity is removed by 4.8 degrees. The electrocatalysis-ozone coupling system taking MnOx-Ti as the cathode has great advantages in the performance of deeply treating pollutants.
The above description is illustrative of the present invention and its embodiments, and is not to be construed as limiting, and the embodiments shown in the examples are only one embodiment of the present invention, and the actual embodiments are not limited thereto. Therefore, if the person skilled in the art receives the teaching, the embodiment and the embodiment similar to the technical solution should be designed without creativity without departing from the spirit of the invention, and shall fall within the protection scope of the invention.

Claims (10)

1. A printing and dyeing wastewater treatment method of an ozone/electrochemical coupling water treatment system based on a DSA (MnOx-Ti) cathode is characterized by comprising the following steps:
s1, firstly, conveying printing and dyeing wastewater into an electrochemical reactor through a pump;
s2, introducing ozone into the printing and dyeing wastewater to perform ozone catalytic oxidation treatment;
s3, carrying out electrocatalysis treatment on the printing and dyeing wastewater treated in the step S2; wherein the cathode material is MnOx-Ti, the cathode takes a metallic titanium sheet as a matrix, and MnCl is processed by a sol-gel method 4 Brushing on a metal titanium sheet, and putting the titanium sheet into a box-type resistance furnace to prepare the titanium alloy at 350-550 ℃; wherein MnOx is MnO 2 And Mn 3 O 4 A mixture of (a).
2. The printing and dyeing wastewater treatment method of a DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system according to claim 1, wherein in the MnOx-Ti electrode, the aperture of the matrix titanium sheet is 2 μm; the load capacity of MnOx-Ti on the base titanium sheet is 0.35-0.40mg/cm 2 。
3. The printing and dyeing wastewater treatment method of a DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system according to claim 1, wherein before the ozone catalytic oxidation treatment, the pH of the treated wastewater is adjusted to 1-3.
4. According to claim1 the printing and dyeing wastewater treatment method of the ozone/electrochemical coupling water treatment system based on the DSA (MnOx-Ti) cathode is characterized in that O 2 The aeration amount is 1-2mol/L.
5. The printing and dyeing wastewater treatment method of the DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system according to claim 1, wherein the electrolyte is sodium sulfate solution with concentration of 50-60 mmol/L.
6. The printing and dyeing wastewater treatment method of the ozone/electrochemical coupling water treatment system based on the DSA (MnOx-Ti) cathode as claimed in claim 1, wherein the hydraulic retention time is 2-5min.
7. The printing and dyeing wastewater treatment method of the ozone/electrochemical coupling water treatment system based on the DSA (MnOx-Ti) cathode as claimed in claim 1, wherein the constant current is controlled to be 0.75-0.80A.
8. The printing and dyeing wastewater treatment method of DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system as claimed in claim 1, wherein the current density is 35.0A/m 2 -37.0A/m 2 。
9. The printing and dyeing wastewater treatment method of the DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system according to claim 1, wherein the cathode material MnOx-Ti is prepared by the following steps:
s1, pretreatment of a titanium substrate: preparing a NaOH solution with the mass fraction of 40%, then putting the titanium substrate into the solution, cleaning for 60min at 80 ℃, preparing an oxalic acid solution with the mass fraction of 15%, and boiling the titanium substrate treated by the NaOH in the oxalic acid solution for 100min;
the preparation method of the S2 MnOx precursor comprises the following steps: preparing an electrode brush precursor: weighing MnCl 2 Mixing with analytically pure isopropanol and 37% pure hydrochloric acid; then placed in a magnetic stirrer for stirring 24h, obtaining a precursor of the MnOx electrode;
the preparation method of the S3 MnOx-Ti cathode material comprises the following steps:
(a) Drying the pretreated titanium substrate by an oven, then placing the dried titanium substrate into a vacuum induction device, sealing and opening a circulating water vacuum pump, and pumping the device to a vacuum state (pumping to the state that a vacuum gauge pointer does not move); then slowly rotating the test tube to enable the brush-coated precursor to flow into the three-neck flask until the liquid level is over the titanium substrate; opening the three-neck flask to release pressure, wherein the brush-coated precursor enters micropores of the titanium substrate, and taking out the titanium substrate to prepare for the next step;
(b) Except in the micropores, the surface of the titanium matrix is coated with a precursor by brush; in order to ensure that the precursor can be uniformly dispersed on the surface of the titanium substrate, the precursor must be slowly and repeatedly brushed during brushing; after the brush coating is finished, putting the mixture into a 105 ℃ drying oven for drying for 10min to volatilize the solvent;
(c) Putting the dried titanium substrate into a box-type resistance furnace at 450 ℃ to sinter for 15min in the air, wherein the heating rate is 5 ℃/min; after repeating the above 3 steps for 21 times, sintering in a box-type resistance furnace at 550 ℃ for 1h.
10. The printing and dyeing wastewater treatment method of DSA (MnOx-Ti) cathode-based ozone/electrochemical coupling water treatment system according to claim 1, wherein the anode material is RuO 2 。
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