CN113354037B - Method for co-treating organic wastewater by oxidation-reduction of nitrogen-doped carbon-based catalytic electrode - Google Patents
Method for co-treating organic wastewater by oxidation-reduction of nitrogen-doped carbon-based catalytic electrode Download PDFInfo
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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
- C02F1/46—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
- C02F1/46—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
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a method for carrying out oxidation-reduction synergistic treatment on organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps: the method is characterized in that a nitrogen-doped carbon-based catalytic electrode is used as an electrode, an oxidant solution, organic wastewater and a reducing agent solution are respectively arranged in an oxidant chamber, an organic wastewater chamber and a reducing agent chamber which are independent, the oxidant chamber and the organic wastewater chamber form a first primary battery system, the organic wastewater chamber and the reducing agent chamber form a second primary battery system, and the organic wastewater is subjected to oxidation-reduction cooperative treatment. The method of the invention separates the reaction medicament from the organic wastewater to be treated, avoids oxidant waste, realizes electrochemical oxidation and electrochemical reduction of organic pollutants in the wastewater by using potential difference, does not need to provide extra voltage, has low treatment cost and obvious advantages in the treatment of high oxidation state organic pollutants.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for treating organic wastewater by the oxidation-reduction cooperation of a nitrogen-doped carbon-based catalytic electrode.
Background
With the development of industry, the problem of water resource shortage is more and more serious, and sewage reuse is an important way for solving the problem. However, organic pollutants in water are low in concentration, difficult to enrich, easy to accumulate biologically and harmful to human health and ecological safety through food chain transmission and other ways, and become a great challenge in the process of sewage recycling.
CN111732262A discloses an electromagnetic enhanced catalytic ozonation device for advanced treatment of organic wastewater and an advanced treatment method of organic wastewater, in which a catalyst layer fixed in the device reacts with ozone and water in the organic wastewater to generate hydroxyl radicals to oxidize and decompose organic pollutants in the organic wastewater, but the method may generate highly toxic by-products after treatment, and requires a motor to generate electromagnetic induction, so that the treatment cost is high.
CN106145537A discloses a method for treating high-concentration organic wastewater by a proton membrane microbial fuel cell, which adopts element-doped titanium dioxide catalyst to carry out photocatalytic reaction, and the filtered wastewater is regulated and then pumped into the microbial fuel cell to carry out anaerobic treatment, and then is adsorbed and filtered by chitosan-modified clay.
CN104787941A discloses an advanced oxidation coupling device and a process for treating refractory organic wastewater, the device comprises an ozone oxidation-multidimensional electrocatalysis/micro-electrolysis area, an ozone oxidation-micro-electrolysis/Fenton area, a coagulation area and an inclined plate sedimentation area, the refractory organic matters are subjected to multi-stage oxidation, and the complete oxidative cracking of the refractory organic matters is realized.
Therefore, how to reduce the consumption of chemicals, reduce the treatment cost and improve the treatment effect while ensuring the degradation efficiency of organic matters becomes a problem which needs to be solved urgently at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for treating organic wastewater by combining oxidation and reduction of a nitrogen-doped carbon-based catalytic electrode, wherein a reaction reagent is separated from the organic wastewater, and electrochemical oxidation and electrochemical reduction are realized by the nitrogen-doped carbon-based catalytic electrode, so that the removal effect of organic pollutants in the wastewater is enhanced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for carrying out oxidation-reduction synergistic treatment on organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps:
the method is characterized in that a nitrogen-doped carbon-based catalytic electrode is used as an electrode, an oxidant solution, organic wastewater and a reducing agent solution are respectively arranged in an oxidant chamber, an organic wastewater chamber and a reducing agent chamber which are independent, the oxidant chamber and the organic wastewater chamber form a first primary battery system, the organic wastewater chamber and the reducing agent chamber form a second primary battery system, and the organic wastewater is subjected to oxidation-reduction cooperative treatment.
The method separates the reaction medicament from the organic wastewater to be treated, thereby avoiding the risk of excess oxidant remaining after wastewater treatment and avoiding the waste caused by the reaction of the oxidant and other ions in water; compared with an electro-Fenton method, the electrochemical oxidation of organic pollutants in the wastewater is realized by utilizing the potential difference, no additional voltage is required to be provided, and the cost is lower; according to the invention, the reducing agent solution is introduced, so that the high oxidation state organic matter can be reduced into the low oxidation state organic matter and then subjected to electrochemical oxidative degradation, and the removal effect of the high oxidation state organic matter is enhanced; compared with a free radical oxidation method, the method has better oxidation selectivity and does not generate high-toxicity byproducts caused by free radical reaction.
Preferably, a first nitrogen-doped carbon-based catalytic electrode is arranged in the oxidant chamber, a second nitrogen-doped carbon-based catalytic electrode and a third nitrogen-doped carbon-based catalytic electrode are arranged in the organic wastewater chamber, and a fourth nitrogen-doped carbon-based catalytic electrode is arranged in the reducing agent chamber.
Preferably, the first nitrogen-doped carbon-based catalytic electrode and the second nitrogen-doped carbon-based catalytic electrode are connected by a first wire.
Preferably, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are connected by a second wire.
The first lead and the second lead are both copper leads which are cheap and easy to obtain, and the organic wastewater treatment cost is reduced.
Preferably, the oxidant chamber and the organic waste water chamber are connected by a first salt bridge.
Preferably, the organic waste water chamber and the reducing agent chamber are connected by a second salt bridge.
The first salt bridge and the second salt bridge in the invention can be selected from agar-saturated potassium sulfate bridges, and compared with the treatment of organic wastewater by adopting an ion exchange membrane, the treatment cost is reduced.
Preferably, the oxidant solution comprises any one or a combination of at least two of a peroxydisulfate solution, a peroxymonosulfate solution, or hydrogen peroxide, wherein typical but non-limiting combinations are a combination of a peroxydisulfate solution and a peroxymonosulfate solution, a combination of a peroxydisulfate solution and hydrogen peroxide, a combination of a peroxydisulfate solution, a peroxymonosulfate solution, and hydrogen peroxide, preferably a sodium peroxydisulfate solution.
Preferably, the concentration of the oxidizing agent solution is 1 to 100mmol/L, for example, 1mmol/L, 2mmol/L, 5mmol/L, 10mmol/L, 15mmol/L, 25mmol/L, 40mmol/L, 50mmol/L, 80mmol/L, 90mmol/L or 100 mmol/L.
Preferably, the organic matter in the organic wastewater comprises phenols and/or nitroaromatics.
Preferably, the organic matter in the organic wastewater further comprises antibiotics and/or hormones.
Preferably, the concentration of the organic matter in the organic wastewater is 0.1 to 20. mu. mol/L, for example, 0.1. mu. mol/L, 0.2. mu. mol/L, 0.5. mu. mol/L, 1. mu. mol/L, 3. mu. mol/L, 5. mu. mol/L, 10. mu. mol/L, 15. mu. mol/L or 20. mu. mol/L.
Preferably, the reducing agent solution comprises a sulfide solution and/or a polysulfide solution, preferably a calcium polysulfide solution.
Preferably, the concentration of the reducing agent solution is 1 to 50mmol/L, for example, 1mmol/L, 2mmol/L, 5mmol/L, 10mmol/L, 15mmol/L, 25mmol/L, 40mmol/L or 50 mmol/L.
Preferably, the volume ratio of the oxidant solution to the organic wastewater to the reductant solution is 1:1: 1-1: 1: 10.
Preferably, the first nitrogen-doped carbon-based catalytic electrode comprises a nitrogen-doped carbon powder modified carbon cloth electrode or a nitrogen-doped carbon powder rolled electrode.
Preferably, the second nitrogen-doped carbon-based catalytic electrode comprises a nitrogen-doped carbon powder modified carbon cloth electrode or a nitrogen-doped carbon powder rolled electrode.
Preferably, the third nitrogen-doped carbon-based catalytic electrode comprises a nitrogen-doped carbon powder modified carbon cloth electrode or a nitrogen-doped carbon powder rolled electrode.
Preferably, the fourth nitrogen-doped carbon-based catalytic electrode comprises a nitrogen-doped carbon powder modified carbon cloth electrode or a nitrogen-doped carbon powder rolled electrode.
The first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode can be different or can adopt the same electrode.
The preparation method of the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode comprises the following steps:
(1) calcining the nitrogen-containing monomer in a muffle furnace at 500 ℃ for 2h to obtain yellow solid carbon nitride; the nitrogen-containing monomer comprises any one of dihydrodiamine, urea or melamine;
(2) mixing the carbon nitride and dopamine hydrochloride according to a mass ratio of 2: 1-1: 2, dispersing by using 100mL of pure water, magnetically stirring for 4 hours, centrifuging, removing a supernatant, and drying in an oven at 80 ℃ to obtain a black solid;
(3) and calcining the black solid in a tubular furnace at 800 ℃ for 2h, and cooling to room temperature to obtain the nitrogen-doped carbon-based catalytic electrode.
The distance between the second nitrogen-doped carbon-based catalytic electrode and the third nitrogen-doped carbon-based catalytic electrode is not particularly required, and the second nitrogen-doped carbon-based catalytic electrode and the third nitrogen-doped carbon-based catalytic electrode are spaced.
Preferably, the specific surface areas of the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are 400-900 m2G, may be, for example, 400m2/g、450m2/g、500m2/g、600m2/g、700m2/g、800m2Per g or 900m2/g。
Preferably, the resistivity of each of the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode, and the fourth nitrogen-doped carbon-based catalytic electrode ranges from 1 to 25 Ω · cm, and may be, for example, 1 Ω · cm, 3 Ω · cm, 5 Ω · cm, 10 Ω · cm, 15 Ω · cm, 20 Ω · cm, or 25 Ω · cm.
The first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode have larger specific surface areas and better adsorption effects, and can be adsorbed before electrochemical oxidation and electrochemical reduction reactions of a primary battery, so that the removal effect of organic pollutants is enhanced.
Preferably, the organic waste water chamber is stirred and mixed in the organic waste water treatment process.
According to the invention, the organic wastewater is stirred and mixed, so that the high-oxidation-state organic pollutants can be reduced in the second primary battery system and then oxidized and decomposed in the first primary battery system, and the removal effect of the high-oxidation-state organic pollutants is improved.
Preferably, the agitating mixing comprises magnetic stirring.
Preferably, the rotation speed of the magnetic stirring is 100-150 rpm, for example, 100rpm, 110rpm, 120rpm, 125rpm, 130rpm, 135rpm, 140rpm, 145rpm or 150rpm can be mentioned.
Preferably, the hydraulic retention time of the organic wastewater is 20-120 min, for example, 20min, 25min, 30min, 40min, 50min, 60min, 80min, 90min, 100min, 110min or 120 min.
As a preferable technical scheme of the method, the treatment method comprises the following steps:
the method comprises the following steps of (1) adopting a nitrogen-doped carbon-based catalytic electrode as an electrode, respectively placing an oxidant solution, organic wastewater and a reducing agent solution in an oxidant chamber, an organic wastewater chamber and a reducing agent chamber which are independent, wherein a first nitrogen-doped carbon-based catalytic electrode is arranged in the oxidant chamber, a second nitrogen-doped carbon-based catalytic electrode and a third nitrogen-doped carbon-based catalytic electrode are arranged in the organic wastewater chamber, and a fourth nitrogen-doped carbon-based catalytic electrode is arranged in the reducing agent chamber; the first nitrogen-doped carbon-based catalytic electrode is connected with the second nitrogen-doped carbon-based catalytic electrode through a first lead; the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are connected through a second lead; the oxidant chamber and the organic wastewater chamber are connected through a first salt bridge; the organic waste water chamber and the reducing agent chamber are connected through a second salt bridge, the oxidant chamber and the organic waste water chamber form a first primary battery system, the organic waste water chamber and the reducing agent chamber form a second primary battery system, and the organic waste water is subjected to oxidation-reduction synergistic treatment; in the process of treating the organic wastewater, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 100-150 rpm, and the hydraulic retention time of the organic wastewater is 20-120 min;
the concentration of the oxidant solution is 1-100 mmol/L; the concentration of the organic matter is 0.1-20 mu mol/L; the concentration of the reducing agent solution is 1-50 mmol/L; the volume ratio of the oxidant solution to the organic wastewater to the reducing agent solution is 1:1: 1-1: 1: 10; the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are respectively and independently any one of nitrogen-doped carbon powder modified carbon cloth or nitrogen-doped carbon powder rolled electrodes; the specific surface areas of the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are 400-900 m2(ii)/g; the resistivity ranges from 1 to 25 omega cm.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for the organic wastewater redox synergistic treatment by the nitrogen-doped carbon-based catalytic electrode, the reaction medicament and the organic wastewater are separated, so that on one hand, the excess oxidant surplus after the wastewater treatment is avoided, and on the other hand, the medicament waste caused by the reaction of the reaction medicament and other ions in water is also avoided;
(2) the method for the oxidation-reduction synergistic treatment of the organic wastewater by the nitrogen-doped carbon-based catalytic electrode utilizes the potential difference to realize the electrochemical oxidation and electrochemical reduction of organic pollutants in the wastewater, does not need to provide extra voltage, and has low treatment cost;
(3) the method for the oxidation-reduction cooperative treatment of the organic wastewater by the nitrogen-doped carbon-based catalytic electrode introduces a reduction reaction reagent, so that the oxidation-reduction cooperative treatment of the low-concentration organic wastewater is realized, and the removal rate of organic pollution reaches above 92.04%.
Drawings
FIG. 1 is a schematic diagram of an apparatus for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode.
In the figure: 1-an oxidant chamber; 2-organic waste water chamber; 3-a reducing agent chamber; 4-a first nitrogen-doped carbon-based catalytic electrode; 5-a second nitrogen-doped carbon-based catalytic electrode; 6-a third nitrogen-doped carbon-based catalytic electrode; 7-a fourth nitrogen-doped carbon-based catalytic electrode; 8-a first copper wire; 9-a second copper wire; 10-a first salt bridge; 11-second salt bridge.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The device schematic diagram of the method for the oxidation-reduction synergistic treatment of organic wastewater by the nitrogen-doped carbon-based catalytic electrode is shown in figure 1.
The device comprises an oxidant chamber 1, an organic waste water chamber 2 and a reducing agent chamber 3 which are independent, wherein a first nitrogen-doped carbon-based catalytic electrode 4 is arranged in the oxidant chamber 1, a second nitrogen-doped carbon-based catalytic electrode 5 and a third nitrogen-doped carbon-based catalytic electrode 6 are arranged in the organic waste water chamber 2, and a fourth nitrogen-doped carbon-based catalytic electrode 7 is arranged in the reducing agent chamber 3; the first nitrogen-doped carbon-based catalytic electrode 4 is connected with the second nitrogen-doped carbon-based catalytic electrode 5 through a first lead 8; the third nitrogen-doped carbon-based catalytic electrode 6 is connected with the fourth nitrogen-doped carbon-based catalytic electrode 7 through a second lead 9; the oxidant chamber 1 and the organic waste water chamber 2 are connected through a first salt bridge 10; the organic waste water chamber 2 and the reducing agent chamber 3 are connected through a second salt bridge 11, so that the oxidant chamber 1 and the organic waste water chamber 2 form a first primary battery system, and the organic waste water chamber 2 and the reducing agent chamber 3 form a second primary battery system.
In an embodiment of the present invention, a method for manufacturing a first nitrogen-doped carbon-based catalytic electrode, a second nitrogen-doped carbon-based catalytic electrode, a third nitrogen-doped carbon-based catalytic electrode, and a fourth nitrogen-doped carbon-based catalytic electrode includes the following steps:
(1) calcining dihydrodiamine in a muffle furnace at 500 ℃ for 2h to obtain yellow solid carbon nitride;
(2) mixing the carbon nitride and the dopamine hydrochloride according to a mass ratio of 2:1, dispersing by using 100mL of pure water, magnetically stirring for 4 hours, centrifuging, removing a supernatant, and drying in an oven at 80 ℃ to obtain a black solid;
(3) and calcining the black solid in a tubular furnace at 800 ℃ for 2h, and cooling to room temperature to obtain the nitrogen-doped carbon-based catalytic electrode.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
The embodiment provides a method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which is carried out by adopting the device in FIG. 1 and comprises the following steps:
50mmol/L sodium persulfate solution is placed in an oxidant chamber provided with a first nitrogen-doped carbon powder modified carbon cloth electrode, 20 mu mol/L p-nitrophenol wastewater is placed in an organic wastewater chamber provided with a second nitrogen-doped carbon powder modified carbon cloth electrode and a third nitrogen-doped carbon powder modified carbon cloth electrode, 5mmol/L calcium polysulfide solution is placed in a reducing agent chamber provided with a fourth nitrogen-doped carbon powder modified carbon cloth electrode, the first nitrogen-doped carbon powder modified carbon cloth electrode and the second nitrogen-doped carbon powder modified carbon cloth electrode are connected by a first copper wire, a first agar-saturated potassium sulfate bridge is connected with the oxidant chamber and the organic wastewater chamber to form a first primary battery system, the third nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are connected by a second copper wire, and the second agar-saturated potassium sulfate bridge is connected with the organic wastewater chamber and the reducing agent chamber to form a second primary battery system, carrying out oxidation-reduction cooperative treatment on the organic wastewater. In the treatment process, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 150rpm, and the hydraulic retention time of the organic wastewater is 120 min.
The first nitrogen-doped carbon powder modified carbon cloth electrode, the second nitrogen-doped carbon powder modified carbon cloth electrode, the third nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are prepared by the preparation method, and the specific surface areas of the electrodes are 795m2The resistivity was 1.79. omega. cm in each case.
The removal results of p-nitrophenol in this example are shown in Table 1.
TABLE 1 removal of p-nitrophenol in the System
| Time (min) | Concentration (μmol/L) | Removal Rate (%) |
| 0 | 20.00 | 0 |
| 10 | 9.10 | 54.50 |
| 20 | 7.52 | 62.40 |
| 40 | 4.31 | 78.45 |
| 60 | 2.93 | 85.35 |
| 80 | 1.25 | 93.75 |
| 100 | 0.84 | 95.80 |
| 120 | 0.69 | 96.55 |
Example 2
The embodiment provides a method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps:
50mmol/L potassium monopersulfate solution is placed in an oxidant chamber provided with a first nitrogen-doped carbon powder rolling electrode, 5 mu mol/L bisphenol A wastewater is placed in an organic wastewater chamber provided with a second nitrogen-doped carbon powder rolling electrode and a third nitrogen-doped carbon powder rolling electrode, 1mmol/L sodium sulfide solution is placed in a reductant chamber provided with a fourth nitrogen-doped carbon powder rolling electrode, the first nitrogen-doped carbon powder rolling electrode and the second nitrogen-doped carbon powder rolling electrode are connected by a first copper wire, a first agar-saturated potassium sulfate bridge is connected with the oxidant chamber and the organic wastewater chamber to form a first primary cell system, the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode are connected by a second copper wire, and a second agar-saturated potassium sulfate bridge is connected with the organic wastewater chamber and the reductant chamber to form a second primary cell system, carrying out oxidation-reduction cooperative treatment on the organic wastewater. In the treatment process, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 150rpm, and the hydraulic retention time of the organic wastewater is 40 min.
The first nitrogen-doped carbon powder rolling electrode, the second nitrogen-doped carbon powder rolling electrode, the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode adopt the preparation methodPrepared by the method, the specific surface area is 567m2(ii)/g; the resistivity was 3.55. omega. cm.
The results of removing bisphenol A in this example are shown in Table 2.
TABLE 2 bisphenol A removal in the System
Example 3
The embodiment provides a method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps:
50mmol/L sodium peroxodisulfate solution is placed in an oxidant chamber provided with a first nitrogen-doped carbon powder rolling electrode, effluent of a secondary sedimentation tank (containing 4.3 mu mol/L ofloxacin) in a sewage treatment structure is placed in an organic wastewater chamber provided with a second nitrogen-doped carbon powder rolling electrode and a third nitrogen-doped carbon powder rolling electrode, 1mmol/L sodium sulfide solution is placed in a reducing agent chamber provided with a fourth nitrogen-doped carbon powder rolling electrode, a first copper lead is used for connecting the first nitrogen-doped carbon powder rolling electrode and the second nitrogen-doped carbon powder rolling electrode, a first agar-saturated potassium sulfate bridge is connected with the oxidant chamber and the organic wastewater chamber to form a first primary battery system, a second lead is used for connecting the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode, and a second agar-saturated potassium sulfate bridge is connected with the organic wastewater chamber and the reducing agent chamber to form a second primary battery system, carrying out oxidation-reduction cooperative treatment on the organic wastewater. In the treatment process, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 150rpm, and the hydraulic retention time of the organic wastewater is 40 min.
The first nitrogen-doped carbon powder rolling electrode, the second nitrogen-doped carbon powder rolling electrode, the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode are prepared by the preparation method, and the specific surface areas of the electrodes are 567m2(ii)/g; the resistivity was 3.55. omega. cm.
The removal of ofloxacin in this example is shown in table 3.
Table 3 ofloxacin removal from the system
Example 4
The embodiment provides a method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps:
1mmol/L potassium peroxymonosulfate solution is placed in an oxidant chamber provided with a first nitrogen-doped carbon powder rolling electrode, 0.1 mu mol/L bisphenol A wastewater is placed in an organic wastewater chamber provided with a second nitrogen-doped carbon powder rolling electrode and a third nitrogen-doped carbon powder rolling electrode, 1mmol/L sodium sulfide solution is placed in a reducing agent chamber provided with a fourth nitrogen-doped carbon powder rolling electrode, a first copper lead is used for connecting the first nitrogen-doped carbon powder rolling electrode and the second nitrogen-doped carbon powder rolling electrode, a first agar-saturated potassium sulfate bridge is connected with the oxidant chamber and the organic wastewater chamber to form a first primary battery system, a second lead is used for connecting the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode, and a second agar-saturated potassium sulfate bridge is connected with the organic wastewater chamber and the reducing agent chamber to form a second primary battery system, carrying out oxidation-reduction cooperative treatment on the organic wastewater. In the treatment process, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 100rpm, and the hydraulic retention time of the organic wastewater is 20 min.
The first nitrogen-doped carbon powder rolling electrode, the second nitrogen-doped carbon powder rolling electrode, the third nitrogen-doped carbon powder rolling electrode and the fourth nitrogen-doped carbon powder rolling electrode are prepared by the preparation method, and the specific surface areas of the electrodes are 567m2(ii)/g; the resistivity was 3.55. omega. cm.
Example 5
The embodiment provides a method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which comprises the following steps:
50mmol/L sodium persulfate solution is placed in an oxidant chamber provided with a first nitrogen-doped carbon powder modified carbon cloth electrode, 20 mu mol/L nitrobenzene wastewater is placed in an organic wastewater chamber provided with a second nitrogen-doped carbon powder modified carbon cloth electrode and a third nitrogen-doped carbon powder modified carbon cloth electrode, 5mmol/L calcium polysulfide solution is placed in a reductant chamber provided with a fourth nitrogen-doped carbon powder modified carbon cloth electrode, the first nitrogen-doped carbon powder modified carbon cloth electrode and the second nitrogen-doped carbon powder modified carbon cloth electrode are connected by a first copper wire, a first agar-saturated potassium sulfate bridge is connected with the oxidant chamber and the organic wastewater chamber to form a first primary cell system, the third nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are connected by a second copper wire, and the second agar-saturated potassium sulfate bridge is connected with the organic wastewater chamber and the reductant chamber to form a second primary cell system, carrying out oxidation-reduction cooperative treatment on the organic wastewater. In the treatment process, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 120rpm, and the hydraulic retention time of the organic wastewater is 120 min.
The first nitrogen-doped carbon powder modified carbon cloth electrode, the second nitrogen-doped carbon powder modified carbon cloth electrode, the third nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are prepared by the preparation method, and the specific surface areas of the electrodes are 795m2(ii)/g; the resistivity of the electrodes was 1.79. omega. cm.
Example 6
This example provides a method for organic wastewater redox-coupled treatment by a nitrogen-doped carbon-based catalytic electrode, which is the same as in example 1 except that the concentration of sodium persulfate is 0.1 mmol/L.
Example 7
This example provides a method for organic wastewater redox-coupled treatment by a nitrogen-doped carbon-based catalytic electrode, which is the same as in example 1 except that the concentration of sodium persulfate is 120 mmol/L.
Second, comparative example
Comparative example 1
The comparative example provides a method for oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode, which is the same as in example 1 except that the first nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are removed.
Comparative example 2
The comparative example provides a method for organic wastewater redox synergistic treatment by a nitrogen-doped carbon-based catalytic electrode, which is the same as that in example 1 except that a fourth nitrogen-doped carbon powder modified carbon cloth electrode is removed.
Comparative example 3
The comparative example provides a method for organic wastewater redox synergistic treatment by using a nitrogen-doped carbon-based catalytic electrode, which is characterized in that a first nitrogen-doped carbon powder modified carbon cloth electrode, a second nitrogen-doped carbon powder modified carbon cloth, a third nitrogen-doped carbon powder modified carbon cloth and a fourth nitrogen-doped carbon powder modified carbon cloth are replaced by graphite plates (the specific surface area of the graphite electrode is 37 m) with the same size2The process is as in example 1 except for the fact that it is used as a reaction product.
Third, test and results
The concentrations of the organic pollutants in the organic wastewater before and after the treatment in examples 1 to 7 and comparative examples 1 to 3 were measured by liquid chromatography, and the removal rate was calculated from the ratio of the difference in the concentrations of the organic pollutants before and after the treatment to the concentration of the organic pollutants before the treatment, and the results are shown in table 4.
TABLE 4 removal of various organics in the System
From table 4, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 7 that the method for the oxidation-reduction synergistic treatment of organic wastewater by the nitrogen-doped carbon-based catalytic electrode can efficiently treat organic wastewater containing p-nitrophenol, bisphenol A, ofloxacin and nitrobenzene, and the removal rate of organic pollutants can reach above 92.04%;
(2) it can be seen from the comprehensive examples 1 and 6 to 7 that, the concentration of sodium persulfate in example 1 is 50mmol/L, and compared with the concentrations of sodium persulfate in examples 6 to 7 of 0.1mmol/L and 120mmol/L respectively, the removal rate of the organic pollutant p-nitrophenol in example 1 can reach 96.55%, the removal rate of the p-nitrophenol in example 6 is reduced to 92.04%, and the removal rate of the p-nitrophenol in example 7 is 98.86%, although the increase of the concentration of the oxidizing agent can improve the removal rate of the organic pollutant, the waste of the chemical agent can be caused, and the treatment cost can be increased, thereby indicating that the concentration of the oxidizing agent solution is further controlled to be 1 to 100mmol/L, which can not only realize the high-efficiency removal of the organic pollutant, but also reduce the consumption of the chemical agent and reduce the treatment cost;
(3) it can be seen from the combination of example 1 and comparative example 1 that, in example 1, the organic pollutant p-nitrophenol is removed by adsorption, and the organic pollutant is removed by electrochemical oxidation and electrochemical reduction, and compared with comparative example 1 in which the first nitrogen-doped carbon powder modified carbon cloth electrode and the fourth nitrogen-doped carbon powder modified carbon cloth electrode are removed, a primary battery system cannot be formed, in comparative example 1, the p-nitrophenol is removed only by adsorption, and the removal rate is only 23.40%, which indicates that the primary battery system is formed by using the nitrogen-doped carbon powder modified carbon cloth electrode, and the removal rate of the organic pollutant is greatly improved;
(4) it can be seen from the combination of the embodiment 1 and the comparative example 2 that the electrochemical oxidation and the electrochemical reduction can be performed simultaneously in the embodiment 1, and compared with the comparative example 2 in which the fourth nitrogen-doped carbon powder modified carbon cloth electrode is removed, and the electrochemical reduction cannot be performed, the removal rate of the p-nitrophenol in the embodiment 1 is much higher than that in the comparative example 2, thereby indicating that the two primary cell systems in the invention realize the oxidation-reduction synergistic treatment of the organic wastewater, and greatly improving the removal effect of the high-oxidation-state organic pollutant p-nitrophenol;
(5) it can be seen from the combination of example 1 and comparative example 3 that, in example 1, the nitrogen-doped carbon powder modified carbon cloth is used as an electrode, and compared with the graphite plate used as an electrode in comparative example 3, the removal rate of p-nitrophenol in example 1 is 96.55%, which is much greater than the removal rate of 8.72% in comparative example 3, which indicates that the nitrogen-doped carbon powder modified carbon cloth electrode is used to form a primary battery system, so that the removal rate of organic pollutants is greatly improved.
In conclusion, the method for the oxidation-reduction synergistic treatment of the organic wastewater by the nitrogen-doped carbon-based catalytic electrode has a good removal effect on organic pollutants, and the removal rate is up to 92.04%; the concentration of the oxidant solution is further controlled to be 1-100 mmol/L, so that the organic pollutants can be efficiently removed, the medicament consumption can be reduced, and the treatment cost is reduced; the method provided by the invention utilizes four nitrogen-doped carbon-based catalytic electrodes to form two primary battery systems, no extra voltage is required to be provided, the organic wastewater is subjected to oxidation-reduction synergistic treatment, and the advantages in the treatment of high-oxidation-state organic pollutants are obvious.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (4)
1. A method for the oxidation-reduction synergistic treatment of organic wastewater by a nitrogen-doped carbon-based catalytic electrode is characterized by comprising the following steps:
the method comprises the following steps of (1) adopting a nitrogen-doped carbon-based catalytic electrode as an electrode, respectively placing an oxidant solution, organic wastewater and a reducing agent solution in an oxidant chamber, an organic wastewater chamber and a reducing agent chamber which are independent, wherein a first nitrogen-doped carbon-based catalytic electrode is arranged in the oxidant chamber, a second nitrogen-doped carbon-based catalytic electrode and a third nitrogen-doped carbon-based catalytic electrode are arranged in the organic wastewater chamber, and a fourth nitrogen-doped carbon-based catalytic electrode is arranged in the reducing agent chamber; the first nitrogen-doped carbon-based catalytic electrode is connected with the second nitrogen-doped carbon-based catalytic electrode through a first lead; the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are connected through a second lead; the oxidant chamber and the organic wastewater chamber are connected through a first salt bridge; the organic waste water chamber and the reducing agent chamber are connected through a second salt bridge, the oxidant chamber and the organic waste water chamber form a first primary battery system, the organic waste water chamber and the reducing agent chamber form a second primary battery system, and the organic waste water is subjected to oxidation-reduction synergistic treatment; in the process of treating the organic wastewater, the organic wastewater chamber is magnetically stirred and mixed at the rotating speed of 100-150 rpm, and the hydraulic retention time of the organic wastewater is 20-120 min;
the oxidant solution is any one or the combination of at least two of peroxydisulfate solution, peroxymonosulfate solution or hydrogen peroxide; organic matters in the organic wastewater are phenols and/or nitroaromatic hydrocarbons; the reducing agent solution is a sulfide solution and/or a polysulfide solution;
the concentration of the oxidant solution is 1-100 mmol/L; the concentration of the organic matter is 0.1-20 mu mol/L; the concentration of the reducing agent solution is 1-50 mmol/L; the volume ratio of the oxidant solution to the organic wastewater to the reducing agent solution is 1:1: 1-1: 1: 10; the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are respectively and independently any one of nitrogen-doped carbon powder modified carbon cloth or nitrogen-doped carbon powder rolled electrodes; the specific surface areas of the first nitrogen-doped carbon-based catalytic electrode, the second nitrogen-doped carbon-based catalytic electrode, the third nitrogen-doped carbon-based catalytic electrode and the fourth nitrogen-doped carbon-based catalytic electrode are 400-900 m2The resistivity ranges from 1 to 25 omega cm;
the preparation method of the nitrogen-doped carbon-based catalytic electrode comprises the following steps:
(1) calcining the nitrogen-containing monomer in a muffle furnace at 500 ℃ for 2h to obtain yellow solid carbon nitride; the nitrogen-containing monomer comprises any one of dihydrodiamine, urea or melamine;
(2) mixing the carbon nitride and dopamine hydrochloride according to a mass ratio of 2: 1-1: 2, dispersing by using 100mL of pure water, magnetically stirring for 4 hours, centrifuging, removing a supernatant, and drying in an oven at 80 ℃ to obtain a black solid;
(3) and calcining the black solid in a tubular furnace at 800 ℃ for 2h, and cooling to room temperature to obtain the nitrogen-doped carbon-based catalytic electrode.
2. The method according to claim 1, characterized in that the oxidant solution is a sodium peroxodisulfate solution.
3. The method according to claim 1, wherein the organic matter in the organic wastewater is antibiotics and/or hormones.
4. The method of claim 1, wherein the reducing agent solution is a calcium polysulfide solution.
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| CN1600699A (en) * | 2004-09-29 | 2005-03-30 | 浙江大学 | Equipment and method for treating organic waste water through electrocatalysis of cathode in combination with anode |
| CN101368278A (en) * | 2007-08-15 | 2009-02-18 | 贾建立 | Method for dismutation electrolytic production of hydrogen, copper, lead, zinc, acid and alkali-chloride by elemental sulfur |
| CN104787851A (en) * | 2014-12-01 | 2015-07-22 | 南京大学 | Electrocatalytic reduction-oxidation reactor and method for pre-treating chlorobenzene waste water using same |
| CN112374601A (en) * | 2020-11-23 | 2021-02-19 | 广东石油化工学院 | Method for degrading organic pollutants in water by using magnetic nitrogen-doped carbon activated persulfate |
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| CN1600699A (en) * | 2004-09-29 | 2005-03-30 | 浙江大学 | Equipment and method for treating organic waste water through electrocatalysis of cathode in combination with anode |
| CN101368278A (en) * | 2007-08-15 | 2009-02-18 | 贾建立 | Method for dismutation electrolytic production of hydrogen, copper, lead, zinc, acid and alkali-chloride by elemental sulfur |
| CN104787851A (en) * | 2014-12-01 | 2015-07-22 | 南京大学 | Electrocatalytic reduction-oxidation reactor and method for pre-treating chlorobenzene waste water using same |
| CN112374601A (en) * | 2020-11-23 | 2021-02-19 | 广东石油化工学院 | Method for degrading organic pollutants in water by using magnetic nitrogen-doped carbon activated persulfate |
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