CN113860436B - Electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode - Google Patents
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Abstract
The invention discloses an electrochemical method for treating copper-containing wastewater by an amidoxime porous carbon electrode, which belongs to the technical field of copper-containing wastewater treatment and comprises the following steps: performing amidoxime reaction on polyacrylonitrile loaded on a porous carbon material to prepare an amidoxime porous carbon electrode, then using the electrode as a cathode, using the porous carbon material as an anode, treating copper-containing wastewater by adopting an electrochemical reaction with asymmetric alternating current, and directly recovering metallic copper on a working electrode; the method successfully recovers copper metal by utilizing the strong chelating property of the amidoxime functional group to copper ions and an electrodeposition method, can reduce the emission concentration of copper ions, is simple to operate, has low cost and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of copper-containing wastewater treatment, and particularly relates to an electrochemical method for treating copper-containing wastewater by using an amidoxime porous carbon electrode.
Background
With the development of economy and industrialization in recent years in China, the domestic electroplating production industry is greatly developed. The electroplating production industry is a heavy pollution industry, and electroplating wastewater generated in the production process contains a large amount of heavy metal ions, for example, toxic and harmful substances such as cadmium, lead, chromium, nickel, copper and other suspended substances, and the direct discharge of the electroplating wastewater can cause serious harm to the ecological environment, so that the electroplating wastewater reaches the discharge standard and needs to be treated.
Copper is in group ib of the fourth period of the periodic table, the most common valence being +2, and often occurs in the form of +2 valence in aqueous solution. Copper and its compounds cause serious pollution to the environment, and the main pollution sources are exploitation and smelting of copper zinc ore, metal processing, mechanical manufacturing, steel production and the like, and smoke dust discharged from smelting is the main source of atmospheric copper pollution. The copper content in the wastewater discharged by the electroplating industry and metal processing is high, and the copper content is tens to hundreds of milligrams per liter of wastewater. Although copper is an essential element of human body, copper pollution in the environment can cause harm to the human body in the very low content of the human body, copper wastewater which is not discharged up to standard can be absorbed by plants in soil and transferred into the human body through a food chain, the content of copper in the human body is about 100-150 mg, and the normal value of serum copper is 100-120 mug/dl.
Current methods for removing copper from wastewater include chemical precipitation, oxidation reduction, membrane filtration and adsorption methods, and common chemical precipitation methods include neutralization precipitation, sulfide precipitation, chelate precipitation and ferrite. However, most of these methods have the disadvantages of secondary pollution and high treatment cost. Redox processes generally have a low effect on copper complex treatment and over time the efficiency of the treatment is significantly reduced. The membrane filtration requires large-scale operation cost and maintenance cost, is not suitable for large-scale application, and the adsorbents are generally classified into active carbon adsorbents, mineral material adsorbents and biological adsorbents, and the adsorption method is simple to operate, but has high cost and short service life, and is not beneficial to large-scale engineering application. Therefore, further research is still needed on how to simply and efficiently remove copper from wastewater.
Disclosure of Invention
In order to solve the technical problems, the invention provides an electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode, which comprises the steps of carrying out amidoxime reaction on Polyacrylonitrile (PAN) loaded on a porous carbon material to obtain the amidoxime porous carbon electrode, then taking the electrode as a cathode, taking the porous carbon material as an anode, treating the copper-containing wastewater by using asymmetric alternating current through electrochemical reaction, and directly recovering metallic copper on a working electrode.
The invention is realized by the following technical scheme.
An electrochemical method for treating copper-containing wastewater by an amidoxime porous carbon electrode, comprising the following steps:
s1, preparing an amidoxime porous carbon electrode by carrying out an amidoxime reaction on polyacrylonitrile loaded on a porous carbon material;
s2, performing electrodeposition treatment on the copper-containing wastewater by taking an amidoxime porous carbon electrode as a cathode and a porous carbon material as an anode through asymmetric alternating current, so as to separate out a copper simple substance on the cathode;
the frequency of the asymmetric alternating current is 200-400 Hz, the high potential of the asymmetric alternating current is +3- +7V, the high potential of the asymmetric alternating current accounts for 10% -30%, and the low potential of the asymmetric alternating current is-10-3V.
Preferably, in S2, the metal element in the copper-containing wastewater is copper element only.
Preferably, in S2, the electrodeposition treatment is performed for 2 to 4 hours.
Preferably, in S2, the power supply device used is a function arbitrary waveform generator.
Preferably, in S2, copper wastewater is in a flowing state during the electrodeposition treatment.
Preferably, in S1 and S2, the porous carbon material is a polyacrylonitrile-based carbon felt, carbon foam or graphite felt.
Preferably, the porous carbon material in S1 and the porous carbon material in S2 may be the same or different.
Preferably, the preparation method of the amidoximation porous carbon electrode comprises the following steps:
s11, dissolving dried polyacrylonitrile in N, N-dimethylamide to prepare a coating solution; placing the cleaned porous carbon material into the coating liquid for ultrasonic treatment, and then standing and drying to obtain a polyacrylonitrile-loaded carbon felt;
s12, preparing a mixed aqueous solution of hydroxylamine hydrochloride and sodium carbonate by taking water as a solvent, and then adding an absolute ethyl alcohol additive to prepare a reaction solution; and (3) placing the polyacrylonitrile-loaded porous carbon material prepared in the step (S1) in the reaction solution, and preparing the amidoxime porous carbon electrode through amidoxime reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The amidoxime reaction is carried out on polyacrylonitrile loaded on a porous carbon material to prepare an amidoxime porous carbon electrode, then the electrode is taken as a cathode, an unmodified porous carbon material is taken as an anode, asymmetric alternating current is utilized, copper-containing wastewater is treated by adopting electrochemical reaction, and metallic copper is directly recovered on a working electrode, and the mechanism is as follows:
functionalization of Cu by amidoxime of porous carbon electrode 2+ The method comprises the steps of carrying out electrodeposition treatment on copper-containing wastewater by using asymmetric alternating current with specific surface binding, and carrying out Cu in the copper-containing wastewater 2+ Randomly distributed in the solution; in the second step, ions start to migrate through the shift in voltage to form an electric double layer, adsorbed Cu 2+ Can specifically bind to the electrode surface; third, the bias voltage is reversed, cu is removed 2+ Reducing to zero-valent; fourthly, when the bias voltage is removed, other ions which are not specifically combined are repelled into the solution again, so that the recovery of the metallic copper simple substance is realized; compared with direct current (when the direct current is used for treating high-concentration metal wastewater, the electrodeposition can cause serious water splitting, so that energy is wasted, local pH value in a negative electrode can be increased, metal hydroxide is precipitated, further electrodeposition is hindered), the energy consumption is low in an asymmetric alternating current deposition process, a large amount of hydrogen evolution reaction is avoided in the treatment process, secondary pollution is avoided in the use process, and the method is an ideal method for treating copper-containing wastewater;
(2) The amidoxime reaction is carried out by using the porous carbon material to prepare the amidoxime porous carbon electrode, and the electrode is used as a cathode.
Drawings
FIG. 1 is a graph showing the trend of copper recovery rate with deposition time for the working electrode of example 1 using alternating current;
FIG. 2 is a graph showing the recovery rate of copper with respect to deposition time at the working electrode of comparative example 1 using direct current.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
The invention provides an electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode, which comprises the following steps:
introducing copper-containing wastewater into an electrolytic cell, adopting a double-electrode system, using a function arbitrary waveform generator and asymmetric alternating current, wherein the frequency of the asymmetric alternating current is 200-400 Hz, the high potential of the asymmetric alternating current is +3- +7V, the high potential of the asymmetric alternating current is 10% -30%, the low potential is-10-3V, the electrodeposition time is 2-4 h, and then flushing a working electrode with deionized water, thereby obtaining deposited metallic copper on the working electrode.
The metal element of the copper-containing wastewater is only copper element.
The working electrode is an amidoxime porous carbon electrode prepared by coating PAN solution on a porous carbon material and then carrying out amidoxime reaction, and the electrode is taken as a cathode and a bare porous carbon material electrode is taken as an anode.
The method can improve the current efficiency and reduce the occurrence of side reactions in the electrodeposition process, and the mechanism is as follows: functionalization of Cu by amidoxime of porous carbon electrode 2+ Has surface specific combination, and then uses asymmetric alternating current to carry out electrodeposition treatment on copper-containing wastewater, and in the treatment process, the first step is that Cu in the copper-containing wastewater 2+ Randomly distributed in the solution; in the second step, ions start to migrate through the shift in voltage to form an electric double layer, adsorbed Cu 2+ Can specifically bind to the electrode surface; thirdly, when the bias voltage is reversed, reducing the heavy metal cations to zero valence; fourthly, when the bias voltage is removed, other ions which are not specifically combined are repelled into the solution again, so that the recovery of the metallic copper simple substance is realized; the energy consumption of the asymmetric alternating current electrodeposition process is smallIn the treatment process, a great amount of hydrogen evolution reaction is avoided, secondary pollution is avoided in the use process, and the method is an ideal way for treating copper-containing wastewater.
The porous carbon material is polyacrylonitrile-based carbon felt, foam carbon or graphite felt, and the porous carbon materials used for the cathode and the anode can be the same or different.
Wherein, the amidoximation porous carbon electrode is specifically prepared by the following method:
(1) Cleaning of porous carbon materials
Putting a porous carbon material of 1.7cm multiplied by 2.2cm into a beaker, adding a certain amount of deionized water, ultrasonically cleaning for 5min, then flushing with deionized water for 5 times, putting the porous carbon material into the beaker filled with 2% nitric acid, ultrasonically cleaning for 5min to remove the reducing substances attached to the surface of the porous carbon material, taking out, and then flushing with deionized water for 5 times; finally, placing the porous carbon material into a beaker filled with absolute ethyl alcohol, placing the beaker into an ultrasonic cleaning instrument for ultrasonic cleaning for 5min to remove organic matters attached to the surface of the porous carbon material, taking out the porous carbon material, and then flushing the porous carbon material with ion water for 5 times; and (3) putting the treated porous carbon material into a blast drying box, and drying for 6 hours at 100 ℃ without changing the weight of the porous carbon material.
(2) Drying of Polyacrylonitrile powder
A 100mL beaker was filled with a certain amount of polyacrylonitrile powder (PAN molecular weight 150000), and the beaker was placed in a forced air drying oven at a temperature of 70 ℃ and dried sufficiently for 24 hours until the PAN weight was unchanged, to remove moisture in the PAN.
(3) Preparation of coating liquid
75g of N, N-Dimethylformamide (DMF) was weighed into a 250mL beaker by an electronic balance, 2.5g of dried polyacrylonitrile powder (PAN molecular weight 150000) was weighed, the PAN powder was slowly added to the DMF while stirring with a glass rod, and then the beaker was placed on a magnetic stirrer and sufficiently stirred for 24 hours to dissolve the PAN completely and the solution became pale yellow, to prepare a coating liquid.
(4) PAN supported by porous carbon material
And placing the pretreated porous carbon material into a 250mL beaker filled with the coating liquid, and placing the beaker into an ultrasonic cleaning instrument for ultrasonic treatment for 5min to allow the coating liquid to fully infiltrate into the porous carbon material. And taking out the beaker, and standing for 5min to enable the coating liquid to be deposited and adhered on the porous carbon material. And after standing, taking out the porous carbon material, placing the porous carbon material in an evaporation dish, placing the evaporation dish in a vacuum drying oven, setting the temperature to be 100 ℃, and vacuum drying for 24 hours, wherein the weight of the porous carbon material is not changed any more.
(5) Amidoxime reaction for preparing amidoxime porous carbon electrode
3.5g of hydroxylamine hydrochloride was accurately weighed by an electronic balance, placed in a 250mL beaker, dissolved by adding 100mL of water, 2.65g of sodium carbonate was accurately weighed by an electronic balance, slowly added to the beaker while stirring with a glass rod, so that sodium carbonate was completely dissolved and no bubbles were released, then 10mL of absolute ethanol was added to the beaker as an additive, and then the solution in the beaker was transferred to a 500mL conical flask entirely. And then fixing the conical flask on a constant temperature shaking table, putting the porous carbon material with the coating liquid into the conical flask, fully reacting for 4 hours at 70 ℃, taking out the porous carbon material after the reaction is finished, washing 5 times by deionized water, putting the porous carbon material into an evaporation dish, putting the evaporation dish into a blast drying box, setting the temperature to be 70 ℃, and drying for 24 hours until the weight of the porous carbon material is not changed, so as to prepare the amidoxime porous carbon electrode.
The following detailed description of the above method and effect will be given by way of specific examples, in which the amidoxime porous carbon electrode is prepared by coating a PAN solution with a polyacrylonitrile-based carbon felt and performing an amidoxime reaction, and the electrode is used as a cathode and the bare polyacrylonitrile-based carbon felt electrode is used as an anode.
Example 1
The electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode in the embodiment is characterized by testing the recovery effect of bivalent copper ions under asymmetric alternating current (frequency 400Hz, high potential +5V, 20% in time, low potential-10V, 80% in time), and specifically comprises the following steps:
an amidoxime porous carbon electrode with the size of 1.7cm multiplied by 2.2cm and a bare polyacrylonitrile-based carbon felt electrode are taken as a cathode,The anode was fixed to an electrolytic cell, and 40mL of Cu having a concentration of 1g/L was injected with a syringe 2+ The solution was injected into a plexiglass electrolyzer. The mode of the electric signal generator is changed into an alternating current mode, asymmetric alternating current (frequency 400Hz, high potential +5V, 20% in time, low potential-10V, 80% in time) is used as a power supply, and the solution flows under the action of a pump and is electrolyzed for 4 hours. The copper-containing wastewater to be deposited is a solution obtained by dissolving copper sulfate pentahydrate in water, wherein the concentration of copper element is 1000ppm, and bivalent copper is the main component.
The counter electrode and the working electrode are stainless steel electrode clamps.
Example 2
An electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode, which is different from example 1 in that (frequency 300Hz, high potential +3V, 30% in time, low potential-3V, 70% in time). The recovery rate was 95.74%.
Example 3
An electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode, which is different from example 1 in that (frequency 200Hz, high potential +7V, 10% in time, low potential-10V, 90% in time). The recovery rate was 96.51%.
EXAMPLES 1 to 3 Properties similar to each other, 1 to 2mL of the electrolyte was sampled every hour (containing 0 h) after the start of electrolysis, and Cu was measured by an atomic absorption spectrophotometer, using example 1 alone 2+ Concentration. FIG. 1 is a graph showing the characteristics of the copper removal rate with the electrolysis time when an asymmetric alternating current (frequency 400Hz, high potential +5V, 20% at time, low potential-10V, 80% at time) was applied to the electrolysis of example 1, from which it can be seen that Cu 2+ The removal rate of Cu is gradually increased in the last 1h 2+ The precipitation rate of (2) becomes slower than before because Cu during electrolysis 2+ As the concentration is continuously reduced, the residual copper ions in the electrolytes of 0h, 1h, 2h, 3h and 4h are 1030ppm, 438.05ppm, 131.7ppm, 53.5ppm and 12.05ppm respectively, so that the residual copper ions can be found in asymmetric alternating current (frequency 400Hz, high potential +5V, 20 percent of time, lowThe potential is-10V, and the recovery rate of copper in the solution reaches 98.83 percent, and the recovery effect is good.
Comparative example 1
The comparative example is an electrochemical method for treating copper-containing wastewater by amidoxime porous carbon electrode, and the recovery effect of bivalent copper ions under the direct-current voltage of 2.7V is tested, which is carried out according to the following steps:
an amidoxime axetilation porous carbon electrode with the size of 1.7cm multiplied by 2.2cm and a polyacrylonitrile-based carbon felt electrode are used as a cathode and an anode to be fixed on an electrolytic tank, and 40mL of Cu with the concentration of 1g/L is injected by a syringe 2+ The solution was injected into a plexiglass electrolyzer. The mode of the electric signal generator is adjusted to be a direct current mode, the voltage is adjusted to be 2.7V, the electric signal generator is used as a power supply, and the solution flows under the action of a pump and is electrolyzed for 4 hours. Taking 1-2 mL of electrolyte per hour (containing 0 h) after the start of electrolysis as a sample, and measuring Cu in the sample by using an atomic absorption spectrophotometer 2+ Concentration.
The copper-containing wastewater to be deposited is a solution obtained by dissolving copper sulfate pentahydrate in water, wherein the concentration of copper element is 1000ppm, and bivalent copper is the main component.
The counter electrode and the working electrode are stainless steel electrode clamps.
FIG. 2 is a graph showing the removal rate of Cu with the electrolysis time under the application of a DC voltage of 2.7V, from which Cu is observed with the increase of the electrolysis time 2+ The removal rate of Cu is gradually increased in the last 1h 2+ The precipitation rate of (2) becomes slower than before because Cu during electrolysis 2+ The concentrations decrease continuously, and it can be seen from the figure that the residual copper ions in the electrolyte solutions of 0h, 1h, 2h, 3h and 4h are 1005ppm, 741ppm, 410ppm, 171.5ppm and 44.85ppm respectively. Thus, it was found that the recovery rate of copper in the solution reached 95.54% at a DC voltage of 2.7V. However, it should be noted that when direct current electrolysis is used in comparative example 1, bubbles appear near the electrode, especially hydrogen evolution reaction near the cathode during the treatment, and in order to save energy consumption and avoid side reactions, a low direct current of 2.7V is required, and the recovery rate is 95.54% at low voltage. And is realIn example 1, the asymmetric alternating current is selected to have high electric potential of +5V, 20% in time, low electric potential of-10V and 80% in time, and a large amount of hydrogen evolution reaction does not occur near the electrode under higher voltage, so that the asymmetric alternating current has higher current efficiency and fewer side reactions, and the recovery rate is as high as 98.83%.
Therefore, compared with the prior art, the method has low cost, simple operation for treating copper wastewater and high copper recovery rate; compared with the method adopting direct current treatment in comparative example 1, the method adopting asymmetric alternating current to treat copper wastewater is not limited by low-voltage conditions, can obtain high copper recovery rate even under higher voltage, and has no side reaction, so the method is more suitable for large-scale popularization and application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (5)
1. An electrochemical method for treating copper-containing wastewater by an amidoxime porous carbon electrode, which is characterized by comprising the following steps:
s1, preparing an amidoxime porous carbon electrode by carrying out an amidoxime reaction on polyacrylonitrile loaded on a porous carbon material; the preparation method of the amidoximation porous carbon electrode comprises the following steps:
s11, dissolving dried polyacrylonitrile in N, N-dimethylamide to prepare a coating solution; placing the cleaned porous carbon material into the coating liquid for ultrasonic treatment, and then standing and drying to obtain the polyacrylonitrile-loaded porous carbon material;
s12, preparing a mixed aqueous solution of hydroxylamine hydrochloride and sodium carbonate by taking water as a solvent, and then adding an absolute ethyl alcohol additive to prepare a reaction solution; placing the polyacrylonitrile-loaded porous carbon material prepared in the step S1 into the reaction solution, and preparing an amidoxime porous carbon electrode through amidoxime reaction;
s2, performing electrodeposition treatment on the copper-containing wastewater by taking an amidoxime porous carbon electrode as a cathode and a porous carbon material as an anode through asymmetric alternating current, so as to separate out a copper simple substance on the cathode;
the power supply equipment is a function arbitrary waveform generator, the frequency of the asymmetric alternating current is 400Hz, the high potential of the asymmetric alternating current is +3 to +7V, the time is 10 to 30 percent, and the low potential is-10 to-3V; the electrodeposition treatment time was 4 hours.
2. The electrochemical method for treating copper-containing wastewater by amidoximation of a porous carbon electrode according to claim 1, wherein in S2, the metal element in the copper-containing wastewater is copper only.
3. The electrochemical method for treating copper-containing wastewater by amidoximation of a porous carbon electrode according to claim 1, wherein in S2, the copper wastewater is in a flowing state during the electrodeposition treatment.
4. The electrochemical method for treating copper-containing wastewater by amidoximation of a porous carbon electrode according to claim 1, wherein in S1 and S2, the porous carbon material is a polyacrylonitrile-based carbon felt, carbon foam or graphite felt.
5. An electrochemical process for treating copper-containing wastewater with an amidoximated porous carbon electrode according to claim 4, wherein the porous carbon material in S1 and the porous carbon material in S2 may be the same or different.
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| 偕胺肟基功能高分子膜对铀吸附过程的研究;辛浩波;吴航;杨金凤;;离子交换与吸附(第03期);第259-264页 * |
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