CN-120504372-B - Electrolytic adsorption device and application thereof

Abstract

The invention relates to the technical field of chlorine-containing electronic wastewater treatment, in particular to an electrolytic adsorption device and application thereof. The invention provides an electrolytic adsorption device which comprises an anode and a cathode which are alternately arranged in parallel, wherein the anode comprises an anode substrate and an anode material coated on the surface of the anode substrate, the anode substrate comprises a titanium foil and a titanium dioxide nanotube layer on the surface of the titanium foil, the titanium dioxide nanotube layer is of a three-dimensional array structure, the anode material is a composite material of SnO 2 , sb and RuO 2 , the cathode comprises a cathode substrate and a cathode material coated on the surface of the cathode substrate, and the cathode material is a mixture of a carbon-based material and ferroferric oxide. The electrolytic adsorption device has low cost, does not have strict requirements on chlorine-containing electronic wastewater treatment, and can effectively remove COD and/or has higher recovery rate of heavy metal (Cu 2+ ).

Inventors

• OUYANG KE
• XIE SHAN
• SONG YUXIA
• LONG JIAN
• HUANG CHAO
• WANG HUI
• HU XINJIANG
• CAI JINGJU
• LI MEIFANG

Assignees

• 中南林业科技大学

Dates

Publication Date

20260508

Application Date

20250516

Claims (7)

1. 1. An electroabsorption device is characterized by comprising anodes and cathodes which are alternately arranged in parallel; The anode comprises an anode substrate and an anode material coated on the surface of the anode substrate, wherein the anode substrate comprises a titanium foil and a titanium dioxide nanotube layer on the surface of the titanium foil, and the titanium dioxide nanotube layer is of a three-dimensional array structure, and the anode material is a composite material of SnO 2 , sb and RuO 2 ; the cathode comprises a cathode substrate and a cathode material coated on the surface of the cathode substrate, wherein the cathode material is a mixture comprising a carbon-based material and ferroferric oxide; the mass ratio of SnO 2 , sb and RuO 2 in the composite material of SnO 2 , sb and RuO 2 is 70:10:20; The preparation process of the anode comprises the following steps: Taking titanium foil as a working anode, taking a platinum sheet as a cathode, taking a solution containing fluorine ions as an electrolyte, performing an anodic oxidation reaction, and performing heat treatment to obtain an anode substrate; preparing a precursor solution, wherein solutes in the precursor solution comprise SnCl 4 、SbCl 3 and RuCl 4 , The solvent in the precursor solution is water, Spraying the precursor solution on the surface of the anode substrate, and then carrying out thermal decomposition to obtain the anode; The mass ratio of the carbon-based material to the ferroferric oxide in the cathode material is 100 (2-10); The carbon-based material comprises one or more of activated carbon, carbon nanotubes and carbon black.
2. 2. The electrowinning apparatus of claim 1, wherein the alternating parallel arrangement is repeated 3 times.
3. 3. The electrolytic adsorption device according to claim 1, wherein the mass ratio of the anode material to the anode substrate is (1-10) 100; the length of the titanium dioxide nanotube in the anode substrate is 0.2-41 mu m, the outer diameter is 10-100 nm, and the wall thickness is 10-20 nm.
4. 4. The electrolytic adsorption device according to claim 1, wherein the concentration of fluorine ions in the electrolyte is 0.2 to 2mg/L; the voltage of the anodic oxidation reaction is 10-30V, and the time is 2 hours; the temperature of the heat treatment is 400-600 ℃, and the heat preservation time is 3 hours.
5. 5. The electrowinning apparatus of claim 1, wherein the cathode is prepared by a process comprising the steps of: and coating a dispersion liquid containing ferroferric oxide and a carbon-based material on the surface of a cathode substrate to obtain the cathode.
6. 6. Use of the electroabsorption device according to any one of claims 1-5 for treating chlorine-containing electronic waste water, characterized in that the method of use comprises the following steps: and (3) introducing the chlorine-containing electronic wastewater into the electrolytic adsorption device for treatment.
7. 7. The use according to claim 6, wherein the flow rate of the chlorine-containing electronic wastewater is 0.1-2 ml/min; The working current of the treatment is 2-20 mA/cm 2 , and the voltage is 2V.

Description

Electrolytic adsorption device and application thereof Technical Field The invention relates to the technical field of chlorine-containing electronic wastewater treatment, in particular to an electrolytic adsorption device and application thereof. Background Electronic products are becoming increasingly important in people's daily lives. A Printed Circuit Board (PCB) is used as a substrate for assembling electronic parts, is a core part of an electronic product, has the main functions of connecting various electronic element components through a circuit, plays roles of conducting and transmitting, and is a key electronic interconnection piece of the electronic product. The production process of the electronic components is extremely complex, and wastewater can be generated in different production stages, including strong acid and alkali wastewater, high-concentration organic wastewater, heavy metal wastewater containing copper, zinc, nickel, chromium and the like, and the water quality is complex and the variation range is large. Because of the large number and wide distribution of electronic enterprises at present, the total discharge amount is very large, and high-concentration wastewater containing heavy metals is discharged by up to about 4 hundred million tons each year. The electronic wastewater is wastewater with high CODcr concentration, often reaching 5000-10000 mg/L, even reaching 20000mg/L, and because of complex components and more refractory organic matters, the electronic wastewater is difficult to be properly treated, so that whether the wastewater CODcr can reach the standard for the treatment of the PCB wastewater (100 mg/L) is mainly determined by the effectiveness of the wastewater treatment. From the water pollutant discharge situation, the heavy metal pollutants discharged by the electronic production industry, represented by circuit printed boards (PCBs), account for more than 95% of the total amount. Because of the process requirement, the electronic industrial wastewater such as PCB contains a large amount of chloride ions and heavy metals, the treatment of the chlorine-containing wastewater is a difficult point of the water treatment process for a long time, and the heavy metals have the characteristics of high toxicity, difficult metabolism in the environment, difficult degradation into harmless substances under natural conditions, easy biological enrichment, biological method effect and the like, and can enter human bodies through food chains to cause harm to the health of the human bodies, so the electronic wastewater is one of the industrial wastewater with the most serious environmental pollution and the greatest harm to human beings. After the electronic wastewater is treated by the traditional technology (chemical precipitation, adsorption, biological method and the like), the pollutant concentration index is controlled to be discharged after reaching the discharge requirement, and a large amount of removed heavy metal pollutants are converted into chemical or biological sludge, which essentially converts water pollution into solid waste pollution, so that the heavy metal hazard weightlessness cannot be really solved. On the other hand, "garbage is misplaced resource", the metals in the wastewater are often expensive heavy metals, and if the metals can be effectively recovered, valuable heavy metal resources are recycled, waste is changed into valuable, and the pollution emission and pollution control problems are really controlled from the source. For example, copper ions in the PCB waste liquid usually exist in free state, complex state and other forms, and the copper-containing waste liquid is treated by adopting an electrolytic method, so that the recovery rate of 90% of metallic copper can be achieved, and the method has high economic benefit. Therefore, as the electronic wastewater with larger yield, the recycling of a large amount of heavy metal resources contained in the wastewater can not only improve economic benefits for enterprises, but also realize wastewater recycling to the maximum extent. The problems to be solved in the current electronic wastewater pollution treatment include (1) stable operation of wastewater treatment facilities, stable achievement of chloride ions, COD and heavy metal ions in wastewater required to meet the requirements of the standard for discharge of electroplating pollutants (GB 21900-2008), (2) reduction of operation cost on the basis of reaching standards, improvement of the recycling rate of electroplating wastewater, and (3) recycling of heavy metals/noble metals in the electroplating wastewater, so that the waste is turned into wealth. The traditional treatment process of domestic and foreign electronic wastewater mainly comprises a chemical precipitation method, an ion exchange method, a membrane separation method, an electrolytic method, an adsorption method, a biological treatment method and the like, but the methods have certa