Complex state heavy metal resource recovery method and application based on topological micro-nano electrodes
By using topological micro-nano electrodes modified with conductive polymers and polychelate groups, and applying an alternating electric field, the method effectively addresses the inefficiencies of conventional methods for recovering complex heavy metals from wastewater, achieving efficient and rapid metal recovery.
Patent Information
- Application Number
- JP2024568493
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-05-05
- Filing Date
- 2024-02-02
- Publication Date
- 2025-06-12
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Conventional methods for removing complex heavy metals from wastewater are ineffective due to low efficiency and selectivity, and they fail to recover heavy metals simultaneously with adsorption.
The method involves creating topological micro-nano electrodes by modifying carbon felt with conductive polymers and polychelate groups, which are then applied in an alternating electric field to efficiently recover complex heavy metals from wastewater.
This method enables efficient and rapid recovery of heavy metals, with strong anti-interference ability and the capability to directly obtain pure heavy metals, surpassing the limitations of conventional adsorption methods.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of environmental protection, and relates to a method for resource recovery of complex heavy metals based on topological micro-nano electrodes and its applications.
Background Art
[0002] Due to the rapid development of industrial activities, especially those in electroplating, metal finishing, leather-making, photography, dye and textile industries, the emissions of heavy metal pollutants are increasing. In addition, untreated irrigation wastewater increases the accumulation of heavy metal concentrations in the soil. The US Environmental Protection Agency has pointed out that complexes of lead (Pb 2+ ) and cadmium (Cd 2+ ) are highly toxic substances. Complex lead can damage the kidneys, central nervous system, liver, and reproductive system, and strongly bind to serum proteins in the blood, potentially altering the functional properties of serum proteins. Complex cadmium is classified as a potentially carcinogenic substance in humans and can lead to kidney dysfunction upon long-term exposure. Therefore, proceeding with the removal of complex heavy metals in wastewater is an important means to avoid the entry of heavy metals into the soil and the food chain.
[0003] Methods for removing heavy metal ions include ion exchange, solvent extraction, electrochemical reduction, membrane separation, and adsorption. In the case of complex heavy metals, conventional methods are mostly ineffective. Adsorption is considered to be a simple and effective method for removing complex heavy metal pollutants, but due to its low efficiency and selectivity, it often fails to meet the requirements. In addition, in conventional adsorption, the adsorption and separation of heavy metals cannot be carried out simultaneously, and the adsorption capacity and adsorption strength of the adsorbent decrease.
Summary of the Invention
Problems to be Solved by the Invention
[0004] To solve the problems described in the above-mentioned background art, embodiments of the present invention aim to provide a method and application for the resource recovery of complex heavy metals based on topological micro-nano electrodes.
Means for Solving the Problems
[0005] To achieve the above object, the present invention provides the following technical solutions.
[0006] The method for the resource recovery of complex heavy metals based on topological micro-nano electrodes is as follows: After cutting the carbon felt into a size of 5×5 cm, it is washed with 10 - 30 mL of acetone for 1 h, then impregnated with 1 mol / L sulfuric acid for 1 h, boiled with deionized water for 1 h, and ultrasonic waves are applied for 5 min before each exchange. Then, it is left standing in an oven at 60°C for 2 h in step S1. The washed carbon felt electrode is placed in a 0.1 - 0.3 mol / L conductive polymer precursor and a 0.1 - 0.3 mol / L sulfuric acid electrolyte solution, and the first and second cycles are circulated at a scanning rate of 2 - 5 mV / s within a suitable potential scanning range. Further, 18 cycles are circulated at a scanning rate of 10 - 20 mV / s within a suitable potential range to obtain a modified electrode in step S2. The modified electrode obtained in step S2 is placed in a solution containing 0.1 - 0.3 mol / L of polychelate groups, and 15 - 20 cycles are circulated at a scanning rate of 15 - 25 mV / s within a suitable potential range to obtain topological micro-nano electrodes in step S3. Step S4 includes applying the obtained topological micro-nano electrodes to the resource recovery and utilization of heavy metals in wastewater, whereby the effect of efficiently and rapidly recovering heavy metals can be achieved.
[0007] Furthermore, in step S2, the conductive polymer precursor includes one or a mixture of multiple types among aniline, pyrrole, acetylene, and indole.
[0008] Furthermore, in the step S2, in the first and second cycles, the suitable potential ranges are -0.2 to +1V, -0.3 to +0.9V, and -0.5 to +1V.
[0009] Furthermore, in the step S2, in the remaining cycles, the suitable potential ranges are -0.2 to +0.8V, -0.3 to +0.8V, and -0.5 to +0.9V.
[0010] Furthermore, in the step S3, the substance containing a polychelate group includes one or more mixtures of diethylenetriaminepentaacetic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA).
[0011] Furthermore, in the step S3, the suitable potential ranges are -0.8 to +1V, -0.9 to +0.9V, and -1 to +1V.
[0012] Furthermore, the resource recovery and utilization method adopted in the step S4 is micro-nanoelectrode adsorption based on the alternating electric field method.
[0013] Furthermore, the metals recovered in the step S4 include, but are not limited to, Cu, Pb, Cd, etc.
[0014] Furthermore, it provides an application of the complex state heavy metal resource recovery method based on the topological micro-nanoelectrode described in any of the above to the resource recovery of complex state heavy metals in wastewater.
[0015] Compared with the prior art, the beneficial effects of the present invention are as follows.
[0016] The present invention is applicable to the technical field of environmental protection, and provides a method and application for resource recovery of complex state heavy metals based on topological micro-nanoelectrodes. First, a porous material such as carbon felt is selected as the base, and by an electrochemical method, a monomer is polymerized to form a conductive polymer and supported on the base. Next, a polymer compound containing a polychelate group is selected, and under electrochemical action, a functional polymer is further grafted onto the conductive polymer to form topological micro-nano electrodes. Finally, under the action of an alternating electric field, the obtained topological micro-nano electrodes are applied to the resource recovery and utilization of complex-state heavy metals in wastewater. The provided synthesis method is simple and easy to perform, the heavy metals can be recovered efficiently and rapidly, the anti-interference ability is strong, and the pure heavy metals can be directly obtained.
Advantages of the Invention
[0017] The advantages of this method are as follows. Regarding the topological micro-nano electrodes, 1. By using carbon felt as the electrode base, the cost is significantly reduced, and the diffusion of complex-state heavy metal wastewater is promoted, making it easier for complex-state heavy metals to contact the active sites on the electrode surface, and enabling efficient resource recovery. 2. The topological micro-nano electrodes are composed of a conductive polymer and a compound containing a polychelate group. The conductive polymer can ensure electron transport and achieve a high current utilization rate, and the compound containing a polychelate group can better bind to complex-state heavy metals, solving the problem of the low adsorption efficiency of conventional adsorbents. 3. The topological microstructure of the topological micro-nano electrodes modifies the surface of the carbon felt to be hydrophilic, making full use of the large surface area of the electrode.
[0018] Regarding the treatment of complex-state heavy metal wastewater by an alternating electric field, 1. By applying an alternating electric field, the negative charge of the DC voltage repels the negative electrode due to Coulomb repulsion, solving problems such as limited electroplated heavy metal cations and large energy loss in the hydraulic crushing process. 2. When the alternating electric field is positive, ions begin to move and form an electric double layer with an inner layer of anions on the surface of the electrode. The chelating sites on the surface of the topological micro-nano electrode compete with the complexing agent to bind to heavy metal cations, stabilizing the heavy metal on the surface of the electrode. 3. When the alternating electric field is negative, heavy metal cations are electrochemically reduced to zero-valent particles. The complexing agent anions lose their affinity for these charge-neutral particles and are repelled by the negative bias. 4. Sodium, magnesium, and calcium ion complexes in wastewater can approach the surface of the electrode when the alternating electric field is positive, but when the alternating electric field is negative, they cannot form zero-valent metals and spontaneously move away from the surface of the electrode, increasing the selectivity and efficiency of electrode formation.
Brief Description of the Drawings
[0019]
Figure 1
Figure 2
Figure 3
Figure 4
Modes for Carrying Out the Invention
[0020] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be described in more detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only for interpreting the present invention and not for limiting the present invention.
[0021] In the following, with reference to specific embodiments, the specific implementation manners of the present invention will be described in detail.
[0022] Example 1 A method for resource recovery of complex-state heavy metals based on topological micro-nano electrodes provided in an embodiment of the present invention includes the following steps. Step S1: After cutting the carbon felt into a size of 5×5 cm, it was washed with 10 mL of acetone for 1 h, then impregnated with 1 mol / L sulfuric acid for 1 h, boiled with deionized water for 1 h, and ultrasonic waves were applied for 5 min before each replacement. Then, it was left standing in an oven at 60 °C for 2 h. Step S2: The washed carbon felt electrode was placed in a 0.1 mol / L aniline and 0.1 mol / L sulfuric acid electrolyte solution, and the first and second cycles were circulated at a scanning rate of 5 mV / s from -0.3 V to +0.9 V. Further, 18 cycles were circulated at a scanning rate of 10 mV / s from -0.1 V to +0.8 V to obtain a modified electrode. Step S3: The modified electrode obtained in Step S2 was placed in a 0.1 mol / L EDTA solution, and 20 cycles were circulated at a scanning rate of 20 mV / s from -1 V to +1 V to obtain a topological micro-nano electrode. Step S4: By applying the obtained topological micro-nano electrode to the resource recovery and utilization of heavy metals in wastewater containing complex-state copper, the effect of efficiently and rapidly recovering heavy metals can be achieved.
[0023] The scanning electron microscope image after the recovery of copper by the topological micro-nano electrode is as shown in Figure 1.
[0024] The removal curves of 1000 mg / L complex-state copper when the alternating electric field method is applied and not applied to the topological micro-nano electrode are as shown in Figure 2.
[0025] The removal curves of 1000 mg / L complex-state copper by the carbon felt and the topological micro-nano electrode are as shown in Figure 3.
[0026] The stability of the removal rate of complex-state copper by topological micro-nano electrodes is as shown in Figure 4.
[0027] Example 2 The method for resource utilization of heavy metals in complex state based on topological micro-nano electrodes provided in an embodiment of the present invention includes the following steps. Step S1: After cutting the carbon felt into a size of 5×5 cm, it was washed with 10 mL of acetone for 1 h, then impregnated with 1 mol / L sulfuric acid for 1 h, boiled with deionized water for 1 h, and ultrasonic waves were applied for 5 min before each replacement. Then, it was left standing in an oven at 60 °C for 2 h. Step S2: The washed carbon felt electrode was placed in a 0.1 mol / L pyrrole and 0.1 mol / L sulfuric acid electrolyte solution, and the first and second cycles were circulated at a scanning rate of 5 mV / s in the range of -0.3 to +0.9 V. Further, 18 cycles were circulated at a scanning rate of 10 mV / s in the range of -0.1 to +0.8 V to obtain a modified electrode. Step S3: The modified electrode obtained in Step S2 was placed in a 0.1 mol / L EDTA solution, and 20 cycles were circulated at a scanning rate of 20 mV / s in the range of -1 to +1 V to obtain a topological micro-nano electrode. Step S4: By applying the obtained topological micro-nano electrode to the resource recovery and utilization of heavy metals in wastewater containing complex-state copper, the effect of efficiently and rapidly recovering heavy metals can be achieved.
[0028] Example 3 The method for resource utilization of heavy metals in complex state based on topological micro-nano electrodes provided in an embodiment of the present invention includes the following steps. Step S1: After cutting the carbon felt into a size of 5×5 cm, it was washed with 10 mL of acetone for 1 h, then impregnated with 1 mol / L sulfuric acid for 1 h, boiled with deionized water for 1 h, and ultrasonic waves were applied for 5 min before each replacement. Then, it was left standing in an oven at 60 °C for 2 h. Step S2: The washed carbon felt electrode was placed in a 0.1 mol / L aniline and 0.1 mol / L sulfuric acid electrolyte solution, and the first and second cycles were circulated at a scanning rate of 5 mV / s in the range of -0.3 to +0.9 V. Further, 18 cycles were circulated at a scanning rate of 10 mV / s in the range of -0.1 to +0.8 V to obtain a modified electrode. Step S3: The modified electrode obtained in Step S2 was placed in a 0.1 mol / L DPTA solution, and 20 cycles were circulated at a scanning rate of 20 mV / s in the range of -1 to +1 V to obtain a topological micro-nano electrode. Step S4: By applying the obtained topological micro-nano electrode to the resource recovery and utilization of heavy metals in wastewater containing complex-state copper, the effect of efficiently and rapidly recovering heavy metals was achieved.
[0029] Example 4 A method for resource recovery of complex-state heavy metals based on a topological micro-nano electrode provided in an embodiment of the present invention includes the following steps. Step S1: After cutting the carbon felt into a size of 5×5 cm, it was washed with 10 mL of acetone for 1 h, then impregnated with 1 mol / L sulfuric acid for 1 h, boiled with deionized water for 1 h, and ultrasonic waves were applied for 5 min before each exchange. Then, it was left standing in an oven at 60°C for 2 h. Step S2: The washed carbon felt electrode was placed in a 0.1 mol / L indole and 0.1 mol / L sulfuric acid electrolyte solution, and the first and second cycles were circulated at a scanning rate of 5 mV / s in the range of -0.3 to +0.9 V. Further, 18 cycles were circulated at a scanning rate of 10 mV / s in the range of -0.1 to +0.8 V to obtain a modified electrode. Step S3: The modified electrode obtained in Step S2 was placed in a 0.1 mol / L DPTA solution, and 20 cycles were circulated at a scanning rate of 20 mV / s in the range of -1 to +1 V to obtain a topological micro-nano electrode. Step S4: By applying the obtained topological micro-nano electrode to the resource recovery and utilization of heavy metals in wastewater containing complex-state copper, the effect of efficiently and rapidly recovering heavy metals was achieved.
[0030] The above description is only a preferred embodiment of the present invention. It should be pointed out that those skilled in the art can also make some modifications and improvements without departing from the concept of the present invention, and these should also be regarded as within the protection scope of the present invention, and none of them will affect the implementation effect of the present invention and the practicality of the patent.
Claims
1. After cutting carbon felt into a size of 5 x 5 cm, it is washed with 10 to 30 mL of acetone for 1 hour, then impregnated with 1 mol / L sulfuric acid for 1 hour, boiled in deionized water for 1 hour, and before each replacement, ultrasonic waves are applied for 5 minutes, and then it is left to stand in a 60 ° C. oven for 2 hours in step S1; Step S2: immerse the washed carbon felt electrode in a 0.1-0.3 mol / L conductive polymer precursor and 0.1-0.3 mol / L sulfuric acid electrolyte solution, cycle the first and second cycles at a scanning rate of 2-5 mV / s in a suitable potential range, and further cycle 18 times at a scanning rate of 10-20 mV / s in a suitable potential range to obtain a modified electrode; Step S3: placing the modified electrode obtained in step S2 in a solution containing 0.1-0.3 mol / L of a polychelate group, and cycling it at a scanning rate of 15-25 mV / s in a suitable potential range for 15-20 cycles to obtain a topological micro-nanoelectrode; Step S4, in which the obtained topological micro-nanoelectrode is applied to the recovery and utilization of complexed heavy metals in wastewater, thereby achieving the effect of recovering heavy metals efficiently and quickly; A method for producing a complex state heavy metal resource based on a topological micro / nanoelectrode, comprising:
2. The method for producing complex-state heavy metals based on topological micro-nano electrodes according to claim 1, characterized in that in step S2, the conductive polymer precursor comprises a mixture of one or more of aniline, pyrrole, acetylene, and indole.
3. The method for producing complex state heavy metal resources based on topological micro-nanoelectrodes according to claim 1, characterized in that in step S2, the suitable potential ranges in the first and second cycles are -0.2 to +1 V, -0.3 to +0.9 V, and -0.5 to +1 V.
4. The method for producing complex state heavy metals based on topological micro-nanoelectrodes according to claim 1, characterized in that in step S2, the suitable potential ranges in the remaining cycles are -0.2 to +0.8 V, -0.3 to +0.8 V, and -0.5 to +0.9 V.
5. The method for producing complex-state heavy metals based on topological micro-nanoelectrodes according to claim 1, characterized in that in step S3, the substance containing a polychelate group comprises one or a mixture of diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA).
6. The method for producing heavy metals in a complex state based on topological micro-nanoelectrodes according to claim 1, characterized in that in step S3, the suitable potential ranges are -0.8 to +1V, -0.9 to +0.9V, and -1 to +1V.
7. The method for recovering and utilizing complex-state heavy metals based on topological micro-nano electrodes as described in claim 1, characterized in that the resource recovery and utilization method adopted in step S4 is micro-nano electrode adsorption based on an alternating electric field method.
8. The method for recovering heavy metals in a complex state based on topological micro-nano electrodes according to claim 1, wherein the metals recovered in step S4 include, but are not limited to, Cu, Pb, Cd, etc.
9. 9. The application of the method for recovering heavy metals in a complex state from wastewater using the topological micro / nanoelectrode according to claim 1 to recover heavy metals in a complex state from wastewater.