CN114149106A - Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation - Google Patents
Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation Download PDFInfo
- Publication number
- CN114149106A CN114149106A CN202111641908.7A CN202111641908A CN114149106A CN 114149106 A CN114149106 A CN 114149106A CN 202111641908 A CN202111641908 A CN 202111641908A CN 114149106 A CN114149106 A CN 114149106A
- Authority
- CN
- China
- Prior art keywords
- coagulation
- treatment
- catalytic oxidation
- water
- tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C02F1/467—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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation, which comprises coagulation treatment, electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment, electro-Fenton treatment and bipolar membrane acid-base regeneration treatment. The method can be carried out under the conditions of normal temperature and normal pressure without regulating pH, and can effectively absorb tail gas generated in the electrochemical reaction without generating secondary pollution; in the process of treating the high-salinity wastewater, soluble salts such as sodium chloride, sodium sulfate and the like do not need to be additionally added; the method is suitable for advanced treatment of COD and ammonia nitrogen in industrial high-salinity wastewater, and has strong oxidation effect and high treatment efficiency.
Description
Technical Field
The invention relates to a treatment technology of organic wastewater, in particular to a treatment method of high-salinity organic wastewater.
Background
With the industrial upgrading of the fields of chemical industry, metallurgy, pharmacy and the like, cleaning wastewater of multiple industries or wastewater treated by multiple process flows is mostly wastewater with higher salinity. The removal of COD and ammonia nitrogen in the industrial high salinity waste water is the problem of puzzlement high salinity waste water advanced treatment and "zero release" always, and how to carry out effective processing and utilization, and then realize water resource high efficiency and utilize and waste water zero release, is the problem that awaits the solution at present.
The organic matter in the high-salinity wastewater is treated by a biological method and a chemical method, wherein the biological method is commonly used for a biofilm method, an activated sludge method and the like, and the chemical method is mainly used for an advanced oxidation method, such as an ozone catalytic oxidation method, a Fenton method, ultraviolet irradiation, a wet oxidation method and the like. The high-salinity wastewater is generally used as the tail end water of industrial water, and due to a series of multiple reactions and process flows in the early stage, various ions in a soluble medicament are gradually accumulated in water level or circulation use, so that the salinity in the water is increased, the effect of treating the wastewater by a common biological method is not obvious, and the effluent cannot achieve the expected effect.
The electrochemical oxidation device is mainly an electrochemical reactor and comprises an external power supply, an electric lead and an electrode. The electric conduction in the aqueous solution is mainly realized through free ions, the high-salinity wastewater contains a large amount of ions, wherein the cations mainly comprise sodium, calcium and the like, the anions mainly comprise chloride ions, sulfate radicals and the like, and the existence of a large amount of ions provides good conditions for electrochemical reaction. The electrochemical method is used for treating the wastewater, mainly through the oxidation reaction of an anode, and can also generate strong oxidation substances (OH, OCl)-、Cl2And) degrading organic matter with large molecule into small molecule matter or mineralizing into CO2And H2And inorganic substances such as O and the like reduce the COD content in the wastewater. The high-salt wastewater contains a large amount of anions (chloride ions and the like), an intermediate product with strong oxidation effect is generated in the chemical oxidation process and is used as an oxidant (the chloride ions generate chlorine gas in the anode through oxidation reaction, the chlorine gas is dissolved in water to generate hypochlorite and chlorate, and the chlorine gas oxidizes reductive substances to play a role in bleaching and sterilizing the wastewater), and the intermediate product and pollutants in the water are subjected to oxidation reaction to be degraded to a certain degree.
Patent publication No. CN101723486A discloses a method for treating wastewater containing salt and chlorine, which comprises the following steps: adjusting the pH value of the wastewater, adding a reduced metal ion catalyst for oxidation treatment, and then adjusting the pH value again for flocculation precipitation in a flocculation tank. The steps of adjusting the pH value twice are complicated, the addition of the reducing metal can not only generate solid waste of metal mud to cause secondary pollution and need secondary treatment, but also discover that the reducing metal can compete with the organic matter and generate oxide through electrochemical reaction according to the comparison of reaction rate constants, so that the removal amount of the organic matter by an electrochemical method is reduced to a certain extent.
Disclosure of Invention
The invention aims to provide a technical scheme for treating high-salinity organic wastewater, namely a method for coagulating-electrochemically catalyzing and oxidizing industrial high-salinity wastewater, which is used for reducing organic matters and ammonia nitrogen in the wastewater, realizing deep treatment of COD (chemical oxygen demand) and ammonia nitrogen in the industrial high-salinity wastewater and realizing the aim of zero discharge of the wastewater. The method for treating the high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation is suitable for wastewater with different pH values, does not need to adjust acid and alkali, and avoids various side reactions. The method is suitable for advanced treatment of COD and ammonia nitrogen in industrial high-salinity wastewater, has strong oxidation effect and high treatment efficiency, and can provide good water inlet guarantee for subsequent advanced treatment. The bipolar membrane method is used for treating the high-salinity wastewater, so that the equipment investment cost is relatively reduced, the energy consumption is low, and the bipolar membrane electrodialysis technology is used for treating the high-salinity wastewater to produce corresponding acid (hydrochloric acid and sulfuric acid) and alkali (sodium hydroxide) while desalting, so that the aim of wastewater treatment can be achieved, and the wastewater recycling is realized. The generated acid and alkali can be used for cleaning equipment and membranes, and can be further concentrated to reach certain purity, so that the resource of waste salt is fully realized, secondary pollution is avoided, economic benefit and environmental benefit are realized, and the method is an economic and environment-friendly wastewater treatment method.
The technical scheme for realizing the invention is as follows: a method for treating high-salinity organic wastewater through coagulation-electrochemical catalytic oxidation is characterized in that organic matters in the high-salinity wastewater are removed after the high-salinity wastewater is subjected to coagulation treatment, electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment, electro-Fenton treatment and a bipolar membrane acid-base regeneration system under the control of a control system, and inorganic matters in the wastewater are prepared into acid and base through a bipolar membrane, and specifically comprises the following steps:
(1) introducing the high-salinity organic wastewater into a coagulation tank, and adding a flocculating agent through a dispensing system for coagulation treatment;
(2) the effluent after coagulation treatment enters an electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank for electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment;
(3) the effluent after electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment enters an electro-Fenton treatment tank for electro-Fenton treatment;
(4) and the effluent after electro-Fenton treatment enters a bipolar membrane acid-base regeneration system to carry out bipolar membrane acid-base regeneration.
Furthermore, the coagulation tank is a reactor with mechanical stirring, the reactor consists of 4 water inlet tanks which are connected through self-overflow, and a stirrer is arranged in each water inlet tank and is used for vertical stirring.
Further, a flocculating agent is added into the water inlet tanks through a metering pump, and 1 multiplied by 10 is added into the first water inlet tank connected through self overflow4-1×107ppm sodium hydroxide, to a second feed tank connected by a self-overflow to which 1X 104-1×107ppm sodium carbonate, added through a third water inlet tank connected by overflow and 1 multiplied by 103-1×106 ppm cationic coagulant, wherein the cationic coagulant comprises inorganic salts, polymeric inorganic salts and metal oxides; adding 1 x 10 water inlet tanks to a fourth water inlet tank connected by self-overflow2-1×106ppm water-soluble long-chain compound flocculant, wherein the water-soluble long-chain compound flocculant comprises polyacrylamide, sodium polyacrylate and polyethyleneimine.
Further, the anode of the electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank is a carbon-based electrode, the cathode is a titanium plate or a titanium plate with a coating, the electrode spacing is 1-2cm, the electrochemical reaction process in the electrochemical catalytic oxidation treatment adopts constant current density to control the electrolytic reaction, and the current density is 400A/m2-1000A/m2The treatment time is60-120 min。
Further, the dosage of the iron carbon particles in the electrolytic cell is 60-90 mg/L.
Further, in order to prevent the acid gas from overflowing the electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank, the electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank is connected with an absorption device, and the absorption liquid in the absorption device adopts a sodium hydroxide solution with the mass concentration of 10-20% as the absorption liquid.
Further, the anode of the electro-Fenton treatment tank is an iron electrode, the cathode is graphite, the distance between the anode plate and the cathode plate is 1-2cm, and the current density is 20A/m2-60 A/m2The reaction time is 60-120 min.
Further, the bipolar membrane acid-base regeneration system adopts a bipolar membrane electrodialysis system, the bipolar membrane electrodialysis system consists of three groups of membrane piles, each group of membrane pile consists of a positive membrane, a negative membrane and a bipolar membrane, and the three groups of membrane piles are connected in series; the water inlet pressure of the membrane stack acid chamber, the alkali chamber and the salt chamber is 1.0-1.2 Mpa, the outlet pressure is 0.4-0.8 Mpa, the water inlet pressure of the polar water is 0.8-1 Mpa, the water outlet pressure is 0.5-0.8 Mpa, and the water inlet flow of the acid chamber, the alkali chamber and the salt chamber is 3-4m3The inlet flow of the polar water is 6-8 m 3H; the transformer in the membrane stack converts the alternating current to direct current, the voltage being in the range of 90-120V at the operating voltage.
Further, in the operation process, the flow and the pressure of the acid chamber, the alkali chamber, the salt chamber and the electrode chamber are kept stable, and then the power supply is turned on; the initial acid concentration of the bipolar membrane electrodialysis system is 0.03-0.05 mol ∙ L-1HCl with an initial base concentration of 0.03 to 0.05 mol ∙ L-1NaOH, 0.2-0.4 mol ∙ L in polar chamber-1 Na2SO4(ii) a In the bipolar membrane acid-base regeneration system, the flow ratio of acid, base and salt is 1:1:1, and the flow of polar water is the sum of the flow of acid and base; the operating current of the bipolar membrane electrodialysis system is kept in a constant current state, and the current density on the membrane is 30-60 mA/cm2The pressure difference between the front and the back of the bipolar membrane electrodialysis membrane is kept within 0.2 Mpa, and the conductivity of the salt room is kept to be more than 10 ms/cm.
Furthermore, flow controllers are arranged at the inlet and outlet of the coagulation tank, the electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank, the electro-Fenton treatment tank and the bipolar membrane electrodialysis system, and are connected with a control system, and the control system can receive the flow change of each unit in real time;
the outlet of the dispensing system, the coagulation tank, the electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank, the electro-Fenton treatment tank and the bipolar membrane electrodialysis system are respectively provided with an online COD detector, an ammonia nitrogen detector, a hardness detector and a conductivity detector, the online COD detector, the ammonia nitrogen detector, the hardness detector and the conductivity detector are connected with a control system, and the control system can control the outlet parameter change of each unit in real time;
the coagulation treatment can adjust the dosage in real time according to the quality of water of intaking under control system's control, the delivery port is equipped with on-line measuring device and can go out water COD, ammonia nitrogen, hardness by real-time detection, can feed back the monitoring value to control system through detection device, control system can adjust the inflow in real time after receiving the signal. When the effluent hardness exceeds the detection value, the control system can control the metering pump, increase the adding amount of sodium hydroxide and sodium carbonate, further reduce calcium and magnesium ions, and ensure the effluent hardness.
The dispensing system can adjust the concentration and flow of the medicament added by the dispensing system in real time according to the quality of inlet water under the control of the control system, so as to achieve the optimal removal effect; the dispensing system contains one or more of inorganic flocculant, inorganic polymeric flocculant, organic cationic polymeric flocculant, organic anionic polymeric flocculant and natural polymeric flocculant, and can be matched with the optimal agent more automatically according to the water quality of inlet water, so as to achieve the optimal removal effect.
The control system can monitor the water quality change of each unit in real time, dynamically adjust the operation of each unit in real time and ensure the normal water outlet index.
The electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank is characterized in that during treatment, the anode is a carbon-based electrode, such as a graphite electrode, the cathode is a titanium plate or a titanium plate with a coating, the shape of the electrode is not specified, other shapes such as a column shape, a sheet shape and the like can be realized, and the distance between the two electrodes in the electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank is 1-2 cm. Electrochemical catalytic oxidation treatmentThe electrochemical reaction process adopts constant current density to control the electrolytic reaction, the control system can adjust different current densities according to the quality of inlet water, and the current density is 400A/m2-1000A/m2. The control system can monitor the change condition of COD and ammonia nitrogen in the treatment tank in real time, and further control the chemical reaction time in the electrochemical catalytic oxidation treatment electrochemical reactor.
The coupling treatment of the electrochemical catalytic oxidation and the iron-carbon microelectrode is to add iron-carbon particles into a coupling treatment tank of the electrocatalytic oxidation and the iron-carbon microelectrode to form the iron-carbon microelectrode in the wastewater, so that the current utilization efficiency is improved, and the treatment effect of the electrocatalytic oxidation is enhanced. The method is characterized in that activated carbon is used as a raw material, ferric chloride and ferrous sulfate are used as iron sources, and the iron and magnetic activated carbon is prepared by using a coprecipitation and calcination method. And then the prepared iron-carbon particles are added into the high-salinity wastewater, and countless micro electric fields formed by the iron-carbon particles in the high-salinity wastewater further degrade organic matters. The magnetic iron-carbon particles are contained, and after the wastewater treatment is finished, the iron-carbon particles can be rapidly recovered through magnetism.
Compared with common activated carbon, the used activated carbon needs to be separated and regenerated, and common separation methods comprise filtration, centrifugation and natural sedimentation. However, these methods are expensive, complicated to operate, slow in settling rate and low in separation efficiency. The magnetic activated carbon prepared by combining the magnetizing agent and the activated carbon is separated by a magnetic field, and the method has the characteristics of simplicity and easiness in operation and can effectively solve the problem of separating the powdered activated carbon. By adding the magnetic activated carbon, the treatment effect is improved, and the problem of activated carbon separation after wastewater treatment is solved.
During the electrochemical catalytic oxidation treatment, 10-20% of sodium hydroxide absorption liquid is connected in order to prevent acid gases such as chlorine gas from overflowing the reactor.
According to the electro-Fenton treatment, the anode electrode is an iron electrode, the cathode is graphite, the control system can control the current density to carry out the electro-Fenton reaction, the reaction time is adjusted according to the water quality of inlet water, the interval between the cathode plate and the anode plate is 1-2cm, and the cathode plate and the anode plate are respectively 50 pieces and are sequentially and alternately combined and arranged. After the wastewater is coupled with an iron-carbon microelectrode through electrochemical catalytic oxidation, organic matters in the wastewater are changed into short chains and cyclic straight chains from long chains. Waste water is treated with electro-Fenton, and hydroxyl radicals generated by electro-Fenton are utilized to directly oxidize organic matters into carbon dioxide, so that the organic matters are removed.
Compared with the prior art, the technical method has the following unique advantages for treating the high-salinity wastewater:
the method is carried out under the conditions of normal temperature and normal pressure without adjusting the pH value; through adding of iron carbon microparticle, can increase tiny electrode at the electricity catalytic oxidation treatment process, further improve the treatment effect, iron carbon particle is magnetic particle, makes things convenient for recycle. No additional soluble salt such as sodium chloride and sodium sulfate is required; the tail gas generated in the electrochemical reaction is effectively absorbed, and no secondary pollution is generated; the process flow is short, the treatment effect is stable, and the operation is convenient; all units can automatically operate under the control of the control system, and the control system can dynamically adjust the inlet and outlet flow and the medicament dosage of each unit in real time according to the change of the water quality of inlet water. Through electrochemical oxidation, macromolecular organic matters can be degraded into micromolecular organic matters, the method is suitable for the subsequent water inlet requirements of deep organic matter removal and desalination treatment devices, and the treatment efficiency of the subsequent process is obviously improved. Compared with the traditional evaporation concentration desalination, the method evaporates the waste water through evaporation crystallization to generate mixed salt such as sodium chloride, sodium sulfate and the like, and the mixed salt needs to be further treated and even needs to be treated as hazardous waste. The bipolar membrane method is used for treating the high-salinity wastewater, so that the equipment investment cost is relatively reduced, the energy consumption is low, and the bipolar membrane electrodialysis technology is used for treating the high-salinity wastewater to produce corresponding acid (hydrochloric acid and sulfuric acid) and alkali (sodium hydroxide) while desalting, so that the aim of wastewater treatment can be achieved, and the wastewater recycling is realized. The generated acid and alkali can be used for cleaning equipment and membranes, and can be further concentrated to reach certain purity, so that the resource of waste salt is fully realized, secondary pollution is avoided, economic benefit and environmental benefit are realized, and the method is an economic and environment-friendly wastewater treatment method.
Drawings
FIG. 1 is a process flow diagram of the coagulation-electrochemical catalytic oxidation treatment of high salinity organic wastewater.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
In the embodiment, the coagulation-electrochemical catalytic oxidation method is adopted to treat the high-salinity pharmaceutical wastewater, and the steps are as follows:
(1) coagulation treatment: the high salinity pharmaceutical wastewater enters the coagulation unit from the water storage tank by a pump. The coagulation unit is a reactor with mechanical stirring, the reactor is 4 water inlet tanks which are connected through self overflow, a stirrer is arranged in each of the 4 water inlet tanks, and the stirrer adopts vertical stirring. Detecting the quality of inlet water by a hardness detector of a control system, wherein the concentration of calcium and magnesium ions in the inlet water is 500ppm, feeding medicine into a pool by a metering pump under the control of a medicine dispensing system, and adding 1 multiplied by 10 into a first inlet water tank connected by self overflow4ppm sodium hydroxide, added through a second inlet tank connected by overflow to 1X 104 ppm sodium carbonate, added through a third water inlet tank connected by overflow and 1 multiplied by 103ppm of aluminum sulfate is added through a fourth water inlet tank which is connected by overflow and is 1 multiplied by 102ppm polyacrylamide. The hardness detector of the control system detects the quality of the inlet water, the concentration of calcium and magnesium ions in the water is 600ppm, and the dispensing system can add 2 multiplied by 10 ions into the first inlet tank which is connected with the dispensing system in a self-overflowing way under the control system4ppm sodium hydroxide, 2X 10 by adding through a second water inlet tank connected with a self-overflow4 ppm sodium carbonate, 2 × 10 is added through a third water inlet tank connected by overflow3ppm of aluminum sulfate is added through a fourth water inlet tank which is connected with an overflow tank by 2 multiplied by 102ppm polyacrylamide.
(2) Electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment: the waste water after coagulation treatment enters an electrolytic bath for electrocatalysis reaction, the anode is a flake graphite electrode, and the cathode is a titanium plate. 60 mg/L of iron-carbon particles are added into an electrolytic cell, the distance between polar plates is 1-2cm, 50 groups of cathode and anode plates are respectively arranged, and the current density is 400A/m2The reaction time was 90 min. The tail gas generated by the reaction is absorbed by 15 percent sodium hydroxide solution. The COD degradation rate is 73.49%, and the ammonia nitrogen concentration is reduced to 10.12 mg/L.
(3) electro-Fenton treatment: after electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment, the wastewater enters an electro-Fenton unit, the anode of the electro-Fenton unit is an iron electrode and a cathode graphite electrode, the cathode and anode plates are respectively 50, and the current density is 20A/m2And reacting for 60 min.
(4) Acid-base regeneration of the bipolar membrane: after electro-Fenton treatment, the COD of the wastewater is reduced to 10 mg/L, and the conductivity of the treated concentrated water is 220 ms/cm. The concentrated water contains a large amount of sodium ions, potassium ions and chlorine plasma, the concentrated water enters a bipolar membrane acid-base regeneration system, namely an electrodialysis acid-base regeneration system, and the initial acid concentration is 0.02 mol ∙ L-1HCl, initial base concentration 0.02 mol ∙ L-1NaOH, 0.3 mol ∙ L in the polar chamber-1 Na2SO4. In the bipolar membrane acid-base regeneration system, the flow ratio of acid, base and salt is 1:1:1, and the flow of polar water is the sum of the flow of acid and base. The operating current of the bipolar membrane electrodialysis system is kept in a constant current state, and the current density on the membrane is 40 mA/cm2The pressure difference between the front and the back of the bipolar membrane electrodialysis membrane is kept within 0.3 Mpa, and the conductivity of the salt room is kept at 220 ms/cm. After the acid-base regeneration of the bipolar membrane, 1.5 mol/L acid and 1.4 mol/L base are prepared.
Example 2
In the embodiment, the coagulation-electrochemical catalytic oxidation method is adopted to treat the reverse osmosis concentrated water of the power plant, and the steps are as follows:
(1) coagulation treatment: the organic wastewater enters the coagulation unit from the water storage tank by a pump. The coagulation unit is a reactor with mechanical stirring, the reactor is 4 water tanks which are connected through self overflow, 4 stirring machines are arranged in the water tanks, and the stirring machines adopt vertical stirring. Detected by a hardness detector of a control systemThe water quality of the inlet water is that the concentration of calcium and magnesium ions in the water is 500ppm, the dosage is fed into the water pool through the metering pump under the control of the dosage system, and 1 multiplied by 10 is added into the first water inlet tank connected through the self-overflow3ppm sodium hydroxide, added through a second inlet tank connected by overflow to 1X 104 ppm sodium carbonate, added through a third water inlet tank connected by overflow and 1 multiplied by 104ppm of aluminum sulfate is added through a fourth water inlet tank which is connected by overflow and is 1 multiplied by 102ppm polyacrylamide.
(2) Electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment: the wastewater after coagulation treatment enters an electrolytic cell for electrocatalysis reaction, the anode is a sheet titanium ruthenium-coated electrode, and the cathode is a titanium plate. The quality of the inlet water is detected by a COD detector and an ammonia nitrogen detector in the detection system, the COD in the water is 6000 mg/L, and the ammonia nitrogen concentration is 30 mg/L. Under the control of a control system, 80 mg/L of iron-carbon particles are added into an electrolytic tank, the distance between polar plates is 1-2cm, 60 groups of cathode and anode plates are respectively arranged, and the current density is 300A/m2The reaction time was 60 min. The tail gas generated by the reaction is absorbed by 15 percent sodium hydroxide solution. The COD degradation rate is 90 percent, and the ammonia nitrogen concentration is reduced to 5 mg/L. The quality of the inlet water is detected by a COD detector and an ammonia nitrogen detector in the detection system, the COD in the water is 7000 mg/L, and the ammonia nitrogen concentration is 40 mg/L. Under the control of a control system, the water inflow is reduced, the treatment time is prolonged, 80 mg/L of iron-carbon particles are added into a wastewater tank, the distance between polar plates is 1-2cm, 60 groups of cathode and anode plates are respectively arranged, and the current density is 300A/m2The reaction time was 70 min. The tail gas generated by the reaction is absorbed by 15 percent sodium hydroxide solution. The COD degradation rate is 92 percent, and the ammonia nitrogen concentration is reduced to 4 mg/L.
(3) electro-Fenton treatment: after electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment, the wastewater enters an electro-Fenton unit, the anode of the electro-Fenton unit is an iron electrode and a cathode graphite electrode, the cathode and anode plates are respectively 50, and the current density is 30A/m2And reacting for 90 min.
(4) Acid-base regeneration of the bipolar membrane: after electro-Fenton treatment, the COD of the wastewater is reduced to 5 mg/L, and the conductivity of the treated concentrated water is 240 ms/cm. The concentrated water contains a large amount of sodium ions and potassium ions, chlorine plasma, and an electrodialytic acid-base regeneration systemThe concentration of the starting acid is 0.03 mol ∙ L-1HCl, initial base concentration 0.03 mol ∙ L-1NaOH, 0.4 mol ∙ L in polar chamber-1 Na2SO4. In the bipolar membrane acid-base regeneration system, acid: alkali: the salt flow ratio is 1:1:1, and the polar water flow is the sum of the acid and alkali flow. The operating current of the bipolar membrane electrodialysis system is kept in a constant current state, and the current density on the membrane is 50 mA/cm2The pressure difference between the front and the back of the bipolar membrane electrodialysis membrane is kept within 0.3 Mpa, and the conductivity of the salt room is kept at 240 ms/cm. After the acid-base regeneration of the bipolar membrane, 1.6 mol/L acid and 1.5 mol/L base are prepared.
Example 3
In the embodiment, the reverse osmosis concentrated water of the coking tail water is treated by adopting a coagulation-electrochemical catalytic oxidation method, and the reverse osmosis concentrated water comprises the following steps:
(1) coagulation treatment: the organic wastewater enters the coagulation unit from the water storage tank by a pump. The coagulation unit is a reactor with mechanical stirring, the reactor is 4 water tanks which are connected through self overflow, 4 stirring machines are arranged in the water tanks, and the stirring machines adopt vertical stirring. Under the control of a dispensing system, the dosage is fed into a water pool through a metering pump, 1 x 104 ppm of sodium hydroxide is added into a first water inlet tank connected through self overflow, 1 x 104 ppm of sodium carbonate is added into a second water inlet tank connected through self overflow, 1 x 103 ppm of aluminum sulfate is added into a third water inlet tank connected through self overflow, and 1 x 102 ppm of polyacrylamide is added into a fourth water inlet tank connected through self overflow.
(2) Electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment: the waste water after coagulation treatment enters an electrolytic bath for electrocatalysis reaction, the anode is a flake graphite electrode, and the cathode is a titanium plate. Adding 90 mg/L iron-carbon particles into the electrolytic cell, wherein the distance between the polar plates is 1-2cm, the cathode and anode plates are respectively divided into 80 groups, and the current density is 500A/m2The reaction time was 120 min. The tail gas generated by the reaction is absorbed by 15 percent sodium hydroxide solution. The COD degradation rate is 98 percent, and the ammonia nitrogen concentration is reduced to 2 mg/L.
(3) electro-Fenton treatment: after electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment, the wastewater enters an electro-Fenton unit, the anode of the electro-Fenton unit is an iron electrode and a cathode graphite electrode, and the cathode and anode plates are respectively provided with 50 pieces of electrodesThe flow density is 60A/m2And reacting for 120 min.
(4) Acid-base regeneration of the bipolar membrane: after electro-Fenton treatment, the COD of the wastewater is reduced to 1 mg/L, and the conductivity of the treated concentrated water is 260 ms/cm. The concentrated water contains a large amount of sodium ions and potassium ions, chlorine plasma and an electrodialytic acid-base regeneration system, and the initial acid concentration is 0.02 mol ∙ L-1HCl, initial base concentration 0.02 mol ∙ L-1NaOH, 0.3 mol ∙ L in the polar chamber-1 Na2SO4. In the bipolar membrane acid-base regeneration system, the flow ratio of acid, base and salt is about 1:1:1, and the flow of polar water is the sum of the flow of acid and base. The operating current of the bipolar membrane electrodialysis system is kept in a constant current state, and the current density on the membrane is 40 mA/cm2The pressure difference between the front and the back of the bipolar membrane electrodialysis membrane is kept within 0.3 Mpa, the conductivity of the salt chamber is kept at 220 ms/cm through an automatic monitoring and control system, and after acid-base regeneration through the bipolar membrane, 1.7mol/L acid and 1.6 mol/L base are prepared.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation is characterized by comprising the following steps:
(1) introducing the high-salinity organic wastewater into a coagulation tank, and adding a flocculating agent through a dispensing system for coagulation treatment;
(2) the effluent after coagulation treatment enters an electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank for electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment;
(3) the effluent after electrochemical catalytic oxidation and iron-carbon microelectrode coupling treatment enters an electro-Fenton treatment tank for electro-Fenton treatment;
(4) and the effluent after electro-Fenton treatment enters a bipolar membrane acid-base regeneration system to carry out bipolar membrane acid-base regeneration.
2. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 1, characterized in that: the coagulation tank is a reactor with mechanical stirring, the reactor consists of 4 water inlet tanks which are connected through self-overflow, and a stirrer is arranged in each water inlet tank and is used for vertical stirring.
3. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 2, characterized in that: adding flocculating agent into the water inlet tank through a metering pump, and adding 1 multiplied by 10 into the first water inlet tank connected through self overflow4-1×107ppm sodium hydroxide, to a second feed tank connected by a self-overflow to which 1X 104-1×107ppm sodium carbonate, added through a third water inlet tank connected by overflow and 1 multiplied by 103-1×106 ppm cationic coagulant, wherein the cationic coagulant comprises inorganic salts, polymeric inorganic salts and metal oxides; adding 1 x 10 water inlet tanks to a fourth water inlet tank connected by self-overflow2-1×106ppm water-soluble long-chain compound flocculant, wherein the water-soluble long-chain compound flocculant comprises polyacrylamide, sodium polyacrylate and polyethyleneimine.
4. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 1, characterized in that: the anode of the electrocatalytic oxidation and iron-carbon microelectrode coupled treatment tank is a carbon-based electrode, the cathode is a titanium plate or a titanium plate with a coating, the electrode distance is 1-2cm, the electrochemical reaction process in the electrochemical catalytic oxidation treatment adopts constant current density to control the electrolytic reaction, and the current density is 400A/m2-1000A/m2The treatment time is 60-120 min.
5. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 4, characterized in that: the dosage of the iron carbon particles in the electrolytic cell is 60-90 mg/L.
6. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 1, characterized in that: in order to prevent the acid gas from overflowing the electrolytic cell, the electrolytic cell is connected with an absorption device, and the absorption liquid in the absorption device adopts a sodium hydroxide solution with the mass concentration of 10-20% as the absorption liquid.
7. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 1, characterized in that: the anode of the electro-Fenton treatment tank is an iron electrode, the cathode is graphite, the distance between the anode plate and the cathode plate is 1-2cm, and the current density is 20A/m2-60 A/m2The reaction time is 60-120 min.
8. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 1, characterized in that: the bipolar membrane acid-base regeneration system adopts a bipolar membrane electrodialysis system, the bipolar membrane electrodialysis system consists of three groups of membrane piles, each group of membrane pile consists of a positive membrane, a negative membrane and a bipolar membrane, and the three groups of membrane piles are connected in series; the water inlet pressure of the membrane stack acid chamber, the alkali chamber and the salt chamber is 1.0-1.2 Mpa, the outlet pressure is 0.4-0.8 Mpa, the water inlet pressure of the polar water is 0.8-1 Mpa, the water outlet pressure is 0.5-0.8 Mpa, and the water inlet flow of the acid chamber, the alkali chamber and the salt chamber is 3-4m3The inlet flow of the polar water is 6-8 m 3H; the transformer in the membrane stack converts the alternating current to direct current, the voltage being in the range of 90-120V at the operating voltage.
9. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to claim 8, characterized in that: in the operation process, firstly, the flow and the pressure of the acid chamber, the alkali chamber, the salt chamber and the polar chamber are kept stable, and then the power supply is switched on; the initial acid concentration of the bipolar membrane electrodialysis system is 0.03-0.05 mol ∙ L-1HCl with an initial base concentration of 0.03 to 0.05 mol ∙ L-1NaOH, 0.2-0.4 mol ∙ L in polar chamber-1 Na2SO4(ii) a In the bipolar membrane acid-base regeneration system, the flow ratio of acid, base and salt is 1:1:1, and the flow of polar water is the sum of the flow of acid and base; the operating current of the bipolar membrane electrodialysis system is kept in a constant current state, and the membraneThe upper current density is 30-60 mA/cm2The pressure difference between the front and the back of the bipolar membrane electrodialysis membrane is kept within 0.2 Mpa, and the conductivity of the salt room is kept to be more than 10 ms/cm.
10. The coagulation-electrochemical catalytic oxidation treatment method for high salinity organic wastewater according to any one of claims 1 to 9, characterized in that: the inlet and outlet of the coagulation tank, the electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank, the electro-Fenton treatment tank and the bipolar membrane electrodialysis system are provided with flow controllers, the flow controllers are connected with a control system, and the control system can receive the flow change of each unit in real time;
the outlet of the dispensing system, the coagulation tank, the electrocatalytic oxidation and iron-carbon microelectrode coupling treatment tank, the electro-Fenton treatment tank and the bipolar membrane electrodialysis system are respectively provided with an online COD detector, an ammonia nitrogen detector, a hardness detector and a conductivity detector, the online COD detector, the ammonia nitrogen detector, the hardness detector and the conductivity detector are connected with a control system, and the control system can control the outlet parameter change of each unit in real time;
the dispensing system can adjust the concentration and flow of the medicament added by the dispensing system in real time according to the quality of inlet water under the control of the control system, so as to achieve the optimal removal effect;
the control system can monitor the water quality change of each unit in real time, dynamically adjust the operation of each unit in real time and ensure the normal water outlet index.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111641908.7A CN114149106A (en) | 2021-12-30 | 2021-12-30 | Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111641908.7A CN114149106A (en) | 2021-12-30 | 2021-12-30 | Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114149106A true CN114149106A (en) | 2022-03-08 |
Family
ID=80449505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111641908.7A Pending CN114149106A (en) | 2021-12-30 | 2021-12-30 | Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149106A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538573A (en) * | 2022-04-26 | 2022-05-27 | 杭州水处理技术研究开发中心有限公司 | Wastewater pre-membrane pretreatment device and pre-membrane pretreatment method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009021396A1 (en) * | 2007-08-10 | 2009-02-19 | Nanjing University | A pretreatment method for coking waste water |
| CN107098527A (en) * | 2017-03-29 | 2017-08-29 | 扬州祥发资源综合利用有限公司 | A kind of method of desulfurization wastewater recycling |
| KR20170125192A (en) * | 2016-05-04 | 2017-11-14 | (주) 가이환경에너지 | Method and apparatus for treatment of treating of non-disintegrating organic waste water using the catalyst |
| CN107585953A (en) * | 2017-09-15 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of benzoic methyl nitroazole method of wastewater treatment |
| CN109879533A (en) * | 2019-03-07 | 2019-06-14 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of Rubber Industrial Wastewater |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN112624446A (en) * | 2020-12-03 | 2021-04-09 | 郑州中科新兴产业技术研究院 | Organic wastewater zero-discharge treatment process |
-
2021
- 2021-12-30 CN CN202111641908.7A patent/CN114149106A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009021396A1 (en) * | 2007-08-10 | 2009-02-19 | Nanjing University | A pretreatment method for coking waste water |
| KR20170125192A (en) * | 2016-05-04 | 2017-11-14 | (주) 가이환경에너지 | Method and apparatus for treatment of treating of non-disintegrating organic waste water using the catalyst |
| CN107098527A (en) * | 2017-03-29 | 2017-08-29 | 扬州祥发资源综合利用有限公司 | A kind of method of desulfurization wastewater recycling |
| CN107585953A (en) * | 2017-09-15 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of benzoic methyl nitroazole method of wastewater treatment |
| CN109879533A (en) * | 2019-03-07 | 2019-06-14 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of Rubber Industrial Wastewater |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN112624446A (en) * | 2020-12-03 | 2021-04-09 | 郑州中科新兴产业技术研究院 | Organic wastewater zero-discharge treatment process |
Non-Patent Citations (1)
| Title |
|---|
| 全国勘察设计注册工程师环保专业管理委员会编: "《中国环境保护产业协会编, 注册环保工程师专业考试复习教材 水污染防治工程技术与实践 中 第4版》", 中国环境出版社, pages: 1304 - 1305 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538573A (en) * | 2022-04-26 | 2022-05-27 | 杭州水处理技术研究开发中心有限公司 | Wastewater pre-membrane pretreatment device and pre-membrane pretreatment method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105601039B (en) | A kind of method for the treatment of of Nitrobenzene class waste water | |
| US6773575B2 (en) | Electrolytic cell and process for the production of hydrogen peroxide solution and hypochlorous acid | |
| EP2050723A1 (en) | Method and integral system for treating water for cooling towers and processess requiring removal of silica from the water | |
| US20120031852A1 (en) | Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes | |
| US20130264197A1 (en) | Nanocatalytic electrolysis and flocculation apparatus | |
| CN108455680B (en) | Environment-friendly resource utilization method of steel pickling waste liquid | |
| Ren et al. | Effective treatment of spacer tube reverse osmosis membrane concentrated leachate from an incineration power plant using coagulation coupled with electrochemical treatment processes | |
| KR20060130455A (en) | Electrodialysis reversal and electrochemical wastewater treatment process of compound containing nitrogen | |
| CN102992523B (en) | Reverse osmosis concentrated wastewater treatment method | |
| CN206014571U (en) | A kind of process complete set of equipments of the nickeliferous waste liquid of PCB factories | |
| CN108358362A (en) | A kind of deep treatment method of high concentrated organic wastewater | |
| CN111470679A (en) | Pretreatment method of waste emulsion | |
| CN112607893A (en) | Plating solution wastewater treatment method for nickel plating of plated part | |
| CN106830467B (en) | Fenton method sewage treatment integrated device based on iron mud recycling and method thereof | |
| JP2017114705A (en) | Method for producing sodium hypochlorite, and sodium hypochlorite production device | |
| CN108358363A (en) | A kind of deep treatment method of organic sewage with high salt | |
| CN107298490B (en) | Electrochemical reactor, method for removing chloride ions in wastewater through electric flocculation, precipitated product and application | |
| CN111422954A (en) | Advanced wastewater treatment method and system for realizing sludge source reduction | |
| JP2018035024A (en) | Method for producing sodium hypochlorite, and sodium hypochlorite production device | |
| CN115745097A (en) | Double-electric Fenton treatment device for high-salt organic wastewater | |
| CN111675394A (en) | High-salt industrial wastewater resource recovery treatment system and method | |
| CN114149106A (en) | Method for treating high-salinity organic wastewater by coagulation-electrochemical catalytic oxidation | |
| CN101811758A (en) | Wastewater treatment method by combination of three-dimensional electrode and electro-Fenton | |
| CN112661359A (en) | System and method for breaking and oxidizing chemical nickel plating residual liquid of vehicle parts | |
| Vasudevan | Can electrochemistry make the worlds water clean?–a systematic and comprehensive overview |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |