Sulfate-containing organic wastewater treatment equipment

Abstract

This utility model discloses a device for treating sulfate-containing organic wastewater, including an electrochemical reaction tank, at least one anode electrode disposed in the electrochemical reaction tank, and at least one cathode electrode disposed in the electrochemical reaction tank. The electrochemical reaction tank is used for in-situ generation of sulfate free radicals. The anode and cathode electrodes are arranged perpendicular to a first direction and alternately in that direction, which is the wastewater flow direction. By setting at least one anode electrode and at least one cathode electrode in the electrochemical reaction tank of the wastewater treatment device, the wastewater can undergo a multi-stage in-situ generation of sulfate free radicals. Arranging the anode and cathode electrodes perpendicular to the wastewater flow direction and alternately in that direction allows for sufficient contact and reaction between the wastewater and the anode and cathode electrodes, further improving wastewater treatment efficiency and ultimately achieving efficient degradation of sulfate-containing organic pollutants in the wastewater.

Description

Technical Field

[0001] This utility model relates to the field of organic wastewater treatment technology, and specifically to a device for treating sulfate-containing organic wastewater. Background Technology

[0002] The primary goal of treating high-salinity organic wastewater is to reduce its COD (Chemical Oxygen Demand). The choice of treatment process depends on factors such as wastewater quality and intended use. Traditional wastewater treatment technologies, such as biochemical methods and membrane separation, are less effective for this type of wastewater. Currently, advanced oxidation technologies (AEOs) offer better results. Among them, electrochemical AEOs directly or indirectly oxidize and degrade organic pollutants in water through redox reactions on electrode surfaces. AEOs have advantages such as high degradation efficiency, low secondary pollution, and strong controllability, and are widely used in the treatment of high-salinity organic wastewater.

[0003] sulfate free radicals (SO4) - Sulfate radicals (·) are free radicals with high redox potentials (E0 = 2.5 eV - 3.1 eV). Under ideal conditions, sulfate radicals are considered capable of oxidizing the vast majority of organic matter. Current advanced electrochemical oxidation technologies primarily use hydroxyl radicals (OH·) as oxidants to mineralize organic matter, mainly targeting wastewater containing easily oxidizable pollutants. Sulfate radicals (SO4·)... - • It can mineralize recalcitrant organic matter and has a long half-life of 4 seconds, which can prolong the contact time with organic matter and improve the degradation effect. It generates sulfate free radicals (SO42-). - There are many methods for generating persulfate radicals, primarily through the activation of persulfate. However, this requires the addition of persulfate reagents in wastewater treatment, increasing the complexity and cost of the process. Some high-salt organic wastewaters contain sulfate ions. If persulfate radicals can be generated in situ in these types of wastewater, it will significantly improve wastewater treatment efficiency and reduce operating costs.

[0004] CN110902776B discloses a method for in-situ electrocatalytic generation of sulfate radicals to oxidize pollutants. This method primarily uses an anode material with a high oxygen evolution potential (OEP) to in-situ activate sulfate in wastewater, generating persulfate ions. The generated persulfate ions are catalyzed into persulfate radicals at the electrocatalytically active anode material. These persulfate radicals participate in the mineralization of pollutants and are then converted back into sulfate. This patent proposes a method for in-situ generation of sulfate radicals, mainly using an anode material with a high OEP (1.8~3V vs. SCE) to synergistically generate sulfate radicals in situ with a cathode. While this patent discloses a method for in-situ generation of sulfate radicals, it only describes the generation method and principle, lacking the design and construction of the apparatus. Utility Model Content

[0005] One of the technical problems this invention aims to solve is: how to design a wastewater treatment device that efficiently degrades sulfate-containing organic pollutants.

[0006] To achieve the above objectives, this utility model provides a sulfate-containing organic wastewater treatment device, including an electrochemical reaction tank, at least one anode electrode disposed in the electrochemical reaction tank, and at least one cathode electrode disposed in the electrochemical reaction tank. The electrochemical reaction tank is used to carry out an in-situ reaction to generate sulfate free radicals. The anode electrode and the cathode electrode are arranged to extend perpendicular to a first direction and are alternately arranged in the first direction, which is the wastewater flow direction.

[0007] In some embodiments, the apparatus further includes a pH adjustment tank disposed upstream of the electrochemical reaction tank, and a connecting pipe is provided between the outlet of the pH adjustment tank and the inlet of the electrochemical reaction tank.

[0008] In some embodiments, the pH adjustment tank includes a pH adjustment vessel and a pH sensor. The pH adjustment vessel is used to contain and adjust the wastewater to be treated, and the pH sensor is located near the connecting pipe for sampling the wastewater in the electrochemical reaction vessel.

[0009] In some embodiments, the pH adjustment tank is connected to an inlet pipe, and an inlet valve is provided on the inlet pipe.

[0010] In some embodiments, a check valve is provided on the connecting pipe.

[0011] In some embodiments, the apparatus further includes a power source disposed outside the electrochemical reaction tank, with the anode electrode connected to the positive terminal of the power source and the cathode electrode connected to the negative terminal of the power source.

[0012] In some embodiments, the electrochemical reaction tank includes a tank body, an anode chamber, and a cathode chamber. The tank body has space for in-situ generation of sulfate radicals. A first end of the anode electrode extends into the tank body and a second end is located in the anode chamber. A first end of the cathode electrode extends into the tank body and a second end is located in the cathode chamber.

[0013] In some embodiments, the electrochemical reaction tank is connected to a water outlet pipe, and a sampling port is provided on the water outlet pipe.

[0014] In some embodiments, the anode electrode is made of one or more of titanium-based platinum group metal oxides, transition metals, BDD materials, and titanium suboxide.

[0015] In some embodiments, the cathode electrode is made of one or more of stainless steel, graphite, and titanium.

[0016] By using the above technical solution, setting at least one anode electrode and at least one cathode electrode in the electrochemical reaction tank of the wastewater treatment device can enable the wastewater to undergo a multi-stage in-situ reaction to generate sulfate free radicals. Setting the anode electrode and cathode electrode to extend perpendicular to the wastewater flow direction and to be arranged alternately in the wastewater flow direction can enable the wastewater to fully contact and react with the anode electrode and cathode electrode, further improving the wastewater treatment efficiency and ultimately achieving efficient degradation of sulfate-containing organic pollutants in the wastewater. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the overall structure of the sulfate-containing organic wastewater treatment device of this utility model.

[0018] Explanation of reference numerals in the attached figures 1. Electrochemical reaction tank; 101. Tank body; 102. Anode chamber; 103. Cathode chamber; 2. Anode electrode; 3. Cathode electrode; 4. pH adjustment tank; 5. Inlet pipe; 6. Outlet pipe; 7. Connecting pipe. Detailed Implementation

[0019] The specific embodiments of this utility model will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the scope of this utility model.

[0020] To address the problem of designing efficient wastewater treatment devices for degrading sulfate-containing organic pollutants in existing technologies, this utility model provides a sulfate-containing organic wastewater treatment device, comprising an electrochemical reaction tank 1, at least one anode electrode 2 disposed in the electrochemical reaction tank 1, and at least one cathode electrode 3 disposed in the electrochemical reaction tank 1. The electrochemical reaction tank 1 is used to carry out a reaction for in-situ generation of sulfate free radicals. The anode electrode 2 and the cathode electrode 3 are arranged to extend perpendicularly to a first direction and are alternately arranged in the first direction, which is the wastewater flow direction.

[0021] like Figure 1 As shown, the principle of this sulfate-containing organic wastewater treatment device is as follows: at least one anode electrode 2 and at least one cathode electrode 3 are set in the electrochemical reaction tank 1 of the wastewater treatment device (the anode electrode 2 is responsible for the oxidation reaction, and the cathode electrode 3 is responsible for the reduction reaction). By allowing the wastewater to be treated to flow through these anode electrodes 2 and 3 in sequence, a multi-stage in-situ reaction to generate sulfate free radicals is carried out. The anode electrode 2 and cathode electrode 3 are set to extend perpendicular to the wastewater flow direction and are arranged alternately in the wastewater flow direction. This allows the wastewater to fully contact and react with the anode electrode 2 and cathode electrode 3, further improving the wastewater treatment efficiency.

[0022] The sulfate radicals generated by the above-mentioned multi-stage in-situ sulfate radical generation reaction have strong oxidizing properties and can efficiently degrade various organic pollutants, achieving thorough purification of wastewater. Ultimately, it achieves efficient degradation of sulfate-containing organic pollutants in wastewater, and the device does not require the addition of additional electrolytes, significantly reducing operating costs.

[0023] This sulfate-containing organic wastewater treatment device is simple to operate and can be well integrated into existing wastewater treatment systems, showing promising application prospects.

[0024] Specifically, the operation steps can be as follows: The pH value of the sulfate-containing organic wastewater is adjusted to (1~7) and then fed into the electrochemical reaction tank 1; When an electric current is applied to the electrochemical reaction tank 1, the organic wastewater passes through the anode electrode 2 and the anode electrode 3. Under the action of the catalyst, the sulfate undergoes electrochemical oxidation, generating highly active sulfate free radicals in situ. The generated sulfate radicals are used to degrade various organic pollutants in the sulfate-containing organic wastewater that is fed into the electrochemical reaction tank 1 through an advanced oxidation process.

[0025] In some embodiments, the apparatus further includes a pH adjustment tank 4 disposed upstream of the electrochemical reaction tank 1, and a connecting pipe 7 is provided between the outlet of the pH adjustment tank 4 and the inlet of the electrochemical reaction tank 1.

[0026] like Figure 1 As shown, the pH adjustment tank 4 contains wastewater to be treated. The flow direction of the wastewater in the pH adjustment tank 4 is set to bottom in and top out, that is, the connecting pipe 7 can be set at the top of the pH adjustment tank 4. The connecting pipe 7 is set to extend horizontally to smoothly transport the wastewater to be treated to the electrochemical reaction tank 1.

[0027] In some embodiments, the pH adjustment tank 4 includes a pH adjustment tank and a pH detection device. The pH adjustment tank is used to contain and adjust the wastewater to be treated, and the pH detection device is located near the connecting pipe 7 for sampling the wastewater in the electrochemical reaction tank 1.

[0028] like Figure 1 As shown, the pH adjustment tank, as a pre-reaction device, can be used to contain the organic wastewater to be treated and serves to connect the inlet pipe 5 and the electrochemical reaction tank 1. A pH sensor is located near the connecting pipe 7 to sample the wastewater from the electrochemical reaction tank 1 within the connecting pipe 7, in order to detect and adjust the pH value of the solution in the electrochemical reaction tank 1 to ensure optimal pH conditions for the reaction. Preferably, the optimal pH value for the reaction in this case is 2.

[0029] In some embodiments, the pH adjustment tank 4 is connected to an inlet pipe 5, and an inlet valve is installed on the inlet pipe 5.

[0030] like Figure 1 As shown, the inlet pipe 5 can be installed at the lower part of the pH adjustment tank 4. The inlet pipe 5 can be further equipped with an inlet valve to control the opening and closing of the inlet pipe 5 and the flow rate of wastewater entering the pH adjustment tank 4.

[0031] In some implementations, a check valve is provided on the connecting pipe 7.

[0032] like Figure 1 As shown, since the pH adjustment tank 4 is the pre-processing device for the electrochemical reaction, a check valve can be installed on the connecting pipe 7 to prevent the solution in the electrochemical reaction tank 1 from flowing back into the pH adjustment tank 4 through the connecting pipe 7 during the reaction. Other regulating valves can also be further installed on the connecting pipe 7 to control the flow rate of wastewater entering the electrochemical reaction tank 1.

[0033] In some embodiments, the apparatus further includes a power source disposed outside the electrochemical reaction tank 1. The anode electrode 2 is connected to the positive terminal of the power source, and the cathode electrode 3 is connected to the negative terminal. The power source (not shown in the figure) is used to connect multiple anode electrodes 2 and multiple cathodes 3 to provide the required voltage and current for the entire electrochemical reaction process. The multiple anode electrodes 2 and multiple cathodes 3 are connected in parallel.

[0034] In some embodiments, the electrochemical reaction tank 1 includes a tank body 101, an anode chamber 102, and a cathode chamber 103. The tank body 101 has space for in-situ generation of sulfate radicals. The first end of the anode electrode 2 extends into the tank body 101 and the second end is located in the anode chamber 102. The first end of the cathode electrode 3 extends into the tank body 101 and the second end is located in the cathode chamber 103.

[0035] like Figure 1 As shown, the electrochemical reaction tank 1 can be composed of three parts: a tank body 101, an anode chamber 102, and a cathode chamber 103. Specifically, the anode chamber 102 and the cathode chamber 103 can be disposed on the side wall of the tank body 101. The anode chamber 102 is used to fix the second end of the anode electrode 2 and isolate it from the solution in the tank body 101, while facilitating the connection of the second end of the anode electrode 2 to an external power source. The remaining part of the anode electrode 2 extends into the tank body 101 through a through hole corresponding to the position of the anode electrode 2. The cathode chamber 103 is used to fix the second end of the cathode electrode 3 and isolate it from the solution in the tank body 101, while facilitating the connection of the second end of the cathode electrode 3 to an external power source. The remaining part of the cathode electrode 3 extends into the tank body 101 through a through hole corresponding to the position of the cathode electrode 3.

[0036] In some embodiments, the electrochemical reaction tank 1 is connected to a water outlet pipe 6, and a sampling port is provided on the water outlet pipe 6. For example... Figure 1As shown, the effluent pipe 6 can be used to discharge wastewater after the in-situ sulfate radical generation reaction into subsequent treatment stages. The effluent pipe 6 can also be equipped with a sampling port to detect the content of organic matter before and after treatment in the wastewater using gas chromatography, thus displaying the organic matter removal rate in the wastewater.

[0037] In some embodiments, the anode electrode 2 is made of one or more of titanium-based platinum group metal oxides, transition metals, BDD materials, and titanium suboxide.

[0038] like Figure 1 As shown, the anode electrode 2 is made of a material with a high oxygen evolution potential (OCE) and is used to activate sulfate in wastewater in situ to generate persulfate ions. Specifically, a special catalyst material with a high OCE (1.8V-3V vs. SCE), such as a BDD electrode plate or titanyl oxide, can be coated onto the anode electrode 2.

[0039] In some embodiments, the cathode electrode 3 is made of one or more of stainless steel, graphite, and titanium.

[0040] like Figure 1 As shown, the cathode electrode 3 works in conjunction with the anode electrode 2 to assist in the electrochemical reaction. The cathode electrode 3 is made of a material with good conductivity, such as stainless steel, graphite, or titanium.

[0041] The following examples illustrate the effectiveness of the sulfate-containing organic wastewater treatment device of this invention.

[0042] Example 1 Anode electrode 2 is made of titanium plate, and cathode electrode 3 is made of stainless steel. In pH adjustment tank 4, the pH of the initial concentration of triethylamine sulfate-containing wastewater (200 mg / L) is adjusted to 1. The current density is controlled at 30 Am / cm² using the electrode power supply. 2 By controlling the influent flow rate, the residence time of the sulfate-containing solution in the electrochemical reaction tank 1 was controlled to 2 hours, and a sampling port was installed in the effluent pipe 6. Gas chromatography was used to detect the content of organic matter before and after the reaction in the wastewater. The results showed that the removal rate of triethylamine in the wastewater reached over 90%.

[0043] Example 2 Anode electrode 2 is a titanium electrode with a titanium suboxide coating, and cathode electrode 3 is made of stainless steel. In pH adjustment tank 4, the pH of the wastewater containing tetrapropylammonium hydroxide sulfate, with an initial concentration of 2000 mg / L, is adjusted to 3. The current density is controlled at 50 Am / cm² using the electrode power supply. 2By controlling the influent flow rate, the residence time of the sulfate-containing solution in the electrochemical reaction tank 1 was controlled to 2 hours. A sampling port was set at the outlet pipe 6. The content of organic matter before and after the wastewater was detected by gas chromatography. The results showed that the removal rate of tetrapropylammonium hydroxide in the wastewater reached more than 95%.

[0044] Example 3 Anode electrode 2 is a BDD-coated electrode, and cathode electrode 3 is a titanium plate. In pH adjustment tank 4, the pH of the sulfate-containing n-butylamine wastewater, initially at a concentration of 5000 mg / L, is adjusted to 5. The current density is controlled at 80 Am / cm² using the electrode power supply. 2 By controlling the influent flow rate, the residence time of the sulfate-containing solution in the electrochemical reaction tank 1 was controlled to 2 hours. A sampling port was provided in the effluent pipe 6. The content of organic matter before and after the wastewater was detected by gas chromatography. The results showed that the removal rate of n-butylamine in the wastewater reached 98%.

[0045] Example 4 Anode electrode 2 is a titanium plate electrode, and cathode electrode 3 is a graphite electrode. In pH adjustment tank 4, the pH of the sulfate-containing ethylenediamine wastewater, initially at a concentration of 10000 mg / L, is adjusted to 6. The current density is controlled at 100 Am / cm² using the electrode power supply. 2 By controlling the influent flow rate, the residence time of the sulfate-containing solution in the electrochemical reaction tank 1 was controlled to 2 hours. A sampling port was provided in the effluent pipe 6. The content of organic matter before and after the wastewater was detected by gas chromatography. The results showed that the removal rate of ethylenediamine in the wastewater reached 80%.

[0046] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings; however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A device for treating sulfate-containing organic wastewater, characterized in that, The device includes an electrochemical reaction tank (1), at least one anode electrode (2) disposed in the electrochemical reaction tank (1), and at least one cathode electrode (3) disposed in the electrochemical reaction tank (1). The electrochemical reaction tank (1) is used to carry out a reaction for in-situ generation of sulfate free radicals. The anode electrode (2) and the cathode electrode (3) are arranged to extend perpendicularly to a first direction and are alternately arranged in the first direction, which is the wastewater flow direction.

2. The sulfuric acid salt-containing organic wastewater treatment apparatus according to claim 1, wherein The device also includes a pH adjustment tank (4) located upstream of the electrochemical reaction tank (1), and a connecting pipe (7) is provided between the outlet of the pH adjustment tank (4) and the inlet of the electrochemical reaction tank (1).

3. The sulfuric acid salt-containing organic wastewater treatment apparatus according to claim 2, wherein The pH adjustment tank (4) includes a pH adjustment tank and a pH detection device. The pH adjustment tank is used to contain and adjust the wastewater to be treated. The pH detection device is located near the connecting pipe (7) and is used to sample the wastewater in the electrochemical reaction tank (1).

4. The sulfuric acid salt-containing organic wastewater treatment apparatus according to claim 2, wherein The pH adjustment tank (4) is connected to an inlet pipe (5), and an inlet valve is installed on the inlet pipe (5).

5. The sulfate-containing organic wastewater treatment device according to claim 2, wherein, A check valve is installed on the connecting pipe (7).

6. The sulfate-containing organic wastewater treatment device according to claim 1, wherein, The device also includes a power source, which is located outside the electrochemical reaction tank (1). The anode electrode (2) is connected to the positive terminal of the power source, and the cathode electrode (3) is connected to the negative terminal of the power source.

7. The sulfate-containing organic wastewater treatment device according to claim 1, wherein, The electrochemical reaction tank (1) includes a tank body (101), an anode chamber (102) and a cathode chamber (103). The tank body (101) has space for in-situ generation of sulfate free radicals. The first end of the anode electrode (2) extends into the tank body (101) and the second end is located in the anode chamber (102). The first end of the cathode electrode (3) extends into the tank body (101) and the second end is located in the cathode chamber (103).

8. The sulfate-containing organic wastewater treatment device according to claim 1, wherein, The electrochemical reaction tank (1) is connected to a water outlet pipe (6), and a sampling port is provided on the water outlet pipe (6).

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