CN115849518A - Transition metal sewage treatment method and transition metal recovery method - Google Patents
Transition metal sewage treatment method and transition metal recovery method Download PDFInfo
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention discloses a transition metal sewage treatment method and a transition metal recovery method. A transition metal sewage treatment method comprises the following steps: under the conditions of light irradiation and electrification, treating the transition metal sewage by using a photocatalytic system comprising a photocatalytic anode, and depositing transition metal on the surface of the photocatalytic anode; the photocatalytic anode comprises conductive glass loaded with a titanium dioxide nanorod array. The transition metal complex breaking process is carried out in the anode chamber, when the photocatalysis anode is under the condition of illumination, photoproduction cavities with strong oxidizing property and active oxygen are generated, the transition metal complex is oxidized to separate organic groups from the transition metal, the organic groups are converted into inorganic matters, thereby realizing the removal of the transition metal complex and simultaneously finishing the deposition of the transition metal on the photoanode.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a transition metal sewage treatment method and a transition metal recovery method.
Background
The nickel has the characteristics of high mechanical strength, corrosion resistance, good ductility, high chemical stability and the like, and the electroplated nickel can form a stable coating on the surface of a plated part, has an ideal protection effect, has a compact and delicate structure, strong corrosion resistance and excellent wear resistance, and is widely applied to the industrial industry. Meanwhile, a large amount of complexing agents are often needed in the production process of the nickel electroplating industry, and heavy metal substances in the wastewater mainly exist in a complexing state. Compared with free heavy metal nickel, the complex heavy metal nickel is firmly combined with a complexing agent ligand and is difficult to be effectively removed by the traditional heavy metal treatment technology, such as alkali precipitation, ion exchange, adsorption and the like. Taking Ni (II) -EDTA as an example, flocculation and ion exchange can only remove 5% of metal complexes, while the membrane filtration and electrodialysis technology can only concentrate sewage, which cannot really realize effective removal of Ni (II) -EDTA and can also generate secondary pollutants such as high-concentration metal complex concentrated solution. Meanwhile, the metal nickel complex is difficult to be intercepted by soil and sediments due to higher stability, and has higher migration capability and long-distance transmission capability than free metal ions in a water environment. Excessive nickel in the water environment can affect the growth and development of plants and even cause the death of the plants; excessive intake of nickel-containing substances can cause nickel poisoning, and serious diseases such as dermatitis, respiratory cancer, and human nervous system degeneration can be caused. Researches show that the metal complex can further improve the biological toxicity of the heavy metal to biological cells, bacteria and plants. After entering the water environment, the nickel complex can be retained in the water environment for a long time due to difficult biodegradation and higher stability, and can be accumulated and transferred in a food chain through the action of biological enrichment, thereby having continuous and profound influence on the ecological environment and the health of human beings. Therefore, a novel nickel complex wastewater treatment technology is developed, the high-efficiency and low-consumption treatment and recycling of the nickel complex wastewater are realized, and the method not only has scientific research value, but also has great environmental significance.
Disclosure of Invention
In order to overcome the problem that the prior art cannot effectively treat the nickel complex wastewater, the invention provides a transition metal wastewater treatment method in a first aspect and a transition metal recovery method in a second aspect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a transition metal sewage treatment method in a first aspect, which comprises the following steps:
under the conditions of light irradiation and electrification, treating the transition metal sewage by using a photocatalytic system comprising a photocatalytic anode, and depositing transition metal on the surface of the photocatalytic anode;
the photocatalytic anode comprises conductive glass loaded with a titanium dioxide nanorod array.
Preferably, in the transition metal wastewater treatment method, the conductive glass comprises at least one of FTO conductive glass and ITO conductive glass.
Preferably, in the transition metal sewage treatment method, the titanium element loading of the photocatalytic anode is 12-20mg/cm 2 (ii) a More preferably, the titanium element loading of the photocatalytic anode is 14-18mg/cm 2 。
Preferably, in the method for treating transition metal wastewater, the transition metal wastewater contains at least one of free metal ions and/or complex metal ions of nickel, copper, manganese and cobalt.
In the invention, transition metal such as manganese (Mn) in the anolyte is utilized to generate photogenerated holes with strong oxidizing property under the condition of illumination of the photocatalytic anode 2+ ) Ion, nickel (Ni) 2+ ) Ion, cobalt (Co) 2+ ) Oxidation to trivalent manganese (Mn) 3+ ) Or tetravalent manganese (Mn) 4+ ) Tetravalent nickel (Ni) 4+ ) Trivalent cobalt (Co) 3+ ) Or tetravalent cobalt (Co) 4+ ) And in the form of a form, a corresponding transition metal-containing oxide is formed and adsorbed on the surface of the photocatalytic anode, so that the selective removal of the transition metal and the enrichment of the transition metal on the surface of the anode are realized.
Preferably, in the method for treating transition metal wastewater, the pH of the transition metal wastewater is 7-12; further preferably, the pH of the transition metal contaminated water is 8 to 9.
Preferably, in the transition metal sewage treatment method, the complexing agent to which the complex-state metal ions are bound comprises at least one of EDTA, phosphate, hydroxycarboxylic acid salt and aminocarboxylic acid salt; further preferably, the complexing agent to which the complexed metal ion is bound is EDTA.
Preferably, in the transition metal sewage treatment method, the light irradiation adopts ultraviolet light; further preferably, the light irradiation is performed by using weak ultraviolet light having a wavelength of 320nm to 400nm.
Preferably, in the transition metal sewage treatment method, direct current is adopted for electrifying; the current density of the direct current is 0.2mA/cm 2 -2.0mA/cm 2 . The current is too small, the complex breaking effect of the transition metal complex in the sewage is not obvious, the transition metal removing effect is not good, the current is too large, although a better complex breaking effect can be achieved, the power source is wasted.
Preferably, in the transition metal sewage treatment method, the time of electrifying and electrolyzing is 120-200min.
Preferably, in the transition metal sewage treatment method, the preparation method of the photocatalytic anode comprises the following steps:
and placing the titanium source solution and the conductive glass into a reaction container, and carrying out hydrothermal reaction to obtain the photocatalytic anode.
Preferably, in the preparation method of the photocatalytic anode, the conductive glass is cleaned before reaction; the cleaning solution can be ultrapure water, acetone, alcohols or a mixed solution of any combination thereof, and the ultrasonic cleaning time is 10-30min.
Preferably, in the preparation method of the photocatalytic anode, the titanium source solution is a tetrabutyl titanate solution, and the concentration of the tetrabutyl titanate solution is 2-4mol/L; further preferably, the concentration of the tetrabutyl titanate solution is 2.5-3.5mol/L; still more preferably, the concentration of the tetrabutyl titanate solution is 2.8 to 3.1mol/L.
Preferably, in the preparation method of the photocatalytic anode, the hydrothermal reaction time is 4-6h; further preferably, the hydrothermal reaction time is 4.5-5.5h.
Preferably, in the preparation method of the photocatalytic anode, the temperature of the hydrothermal reaction is 500-600 ℃; further preferably, the hydrothermal reaction temperature is 520 to 580 ℃.
In a second aspect, the present invention provides a method for recovering a transition metal, comprising the steps of: after the transition metal sewage treatment method is used for treatment, reverse current is applied or the photoanode is taken out and placed in an acid solution, so that the recovery of the transition metal is realized.
The invention has the beneficial effects that:
the transition metal complex breaking process is carried out in the anode chamber, when the photocatalysis anode is under the condition of illumination, photoproduction cavities with strong oxidizing property and active oxygen are generated, the transition metal complex is oxidized to separate organic groups from the transition metal, the organic groups are converted into inorganic matters, thereby realizing the removal of the transition metal complex and simultaneously finishing the deposition of the transition metal on the photoanode.
The invention belongs to photoelectrocatalysis, and can achieve the effect of saving electric energy; and the adoption of electric-assisted photocatalysis can reduce the hole recombination rate, strengthen the generation process of photoproduction holes and improve the treatment efficiency of transition metal ions.
The method can obtain the nickel oxide directly falling off from the surface of the anode when removing high-concentration nickel ions or continuously removing low-concentration nickel ions, and can realize direct recovery.
Drawings
FIG. 1 is a diagram of a photocatalytic system according to an embodiment.
FIG. 2 is a scanning electron micrograph of a photoanode in example 1.
FIG. 3 is a spectrum analysis chart of the photoanode in example 1.
FIG. 4 is a graph showing the tendency of the degradation rate of Ni (II) -EDTA in example 2.
Reference numeral 1:
100-first acrylic plate, 200-first gasket, 300-photoanode, 400-second gasket, 500-anode reaction chamber, 600-third gasket, 700-proton membrane, 800-fourth gasket, 900-cathode reaction chamber, 1000-fifth gasket, and 1100-second acrylic plate.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The photocatalytic system shown in the attached drawing 1 is adopted to treat transition metal sewage, as shown in the attached drawing 1, the whole reactor is assembled, sewage enters from a small hole above an anode reaction chamber 500, a sodium bicarbonate buffer solution is added into a cathode reaction chamber 900, direct current and ultraviolet light are started according to reaction conditions, continuous sampling is carried out on the small hole above the anode reaction chamber 500 during reaction, and after the reaction is finished, the sewage after the reaction is taken out from the small hole above the anode reaction chamber 500 to carry out detection on related data.
Example 1
This example provides FTO deposition of TiO 2 The preparation method of the nanorod array (photo-anode) specifically comprises the following steps:
ultrasonically cleaning FTO conductive glass in a mixed solution (solution concentration does not have requirements) composed of ultrapure water, acetone and isopropanol for 20 minutes, then placing the ultrasonically cleaned FTO conductive glass in the mixed solution of hydrochloric acid, ultrapure water and tetrabutyl titanate (2.94 mol/L), placing the mixed solution into a polytetrafluoroethylene pressure cooker, placing the polytetrafluoroethylene pressure cooker into a drying oven, setting the temperature to be 550 ℃, and carrying out hydrothermal reaction for 5 hours to obtain FTO deposited TiO 2 And (4) a nanorod array photoanode.
The scanning electron micrograph of the photoanode is shown in FIG. 2, and the energy spectrum analysis map is shown in FIG. 3. The photoanode prepared in this example was used in the following examples.
Example 2
A treatment method of sewage containing Ni (II) -EDTA comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photoanode, a platinum electrode is a cathode, 5ppm of Ni-EDTA electrolyte irradiates the photocatalytic anode with 384nm ultraviolet light and is supplemented with 2.8mA direct current, sulfuric acid and sodium hydroxide are used for adjusting the pH of the solution to 8.5, electrolysis is carried out for 150min, the degradation rate of Ni (II) -EDTA can reach 80%, and the recovery rate of the cation deposited nickel can reach 40%.
The invention proceeds with Ni 2+ The ion recovery is carried out in the anode reaction chamber, when the device works, because the alkali metal, the alkaline earth metal ion and the iron ion can not be oxidized by photocatalysis, the deposition of the alkali metal, the alkaline earth metal ion and the iron ion on the electrode can be avoided, and the Ni can be realized 2+ And (4) selectively recovering ions.
The invention utilizes the photocatalysis anode to generate photoproduction holes with strong oxidizing property under the condition of illumination, and divalent nickel (Ni) in the anolyte 2+ ) Ion oxidation to trivalent nickel (Ni) 3+ ) Or tetravalent nickel (Ni) 4+ ) And the corresponding nickel-containing oxide is formed and adsorbed on the surface of the photocatalytic anode, so that the selective removal of the metallic nickel and the enrichment of the nickel on the surface of the anode are realized.
Example 3
A treatment method of sewage containing Ni (II) -EDTA comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photoanode, a platinum electrode is a cathode, 5ppm of Ni (II) -EDTA electrolyte irradiates the photocatalytic anode with 384nm ultraviolet light and is supplemented with 0mA direct current, sulfuric acid and sodium hydroxide are used for adjusting the pH of the solution to 8.5, electrolysis is carried out for 150min, and the degradation rate of Ni (II) -EDTA can reach 10%.
Example 4
A treatment method of sewage containing Ni (II) -EDTA comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photoanode, a platinum electrode is a cathode, 5ppm of Ni (II) -EDTA electrolyte is used for regulating the pH of the solution to 8.5 by using 2.8mA direct current and using sulfuric acid and sodium hydroxide for electrolysis for 150min, the degradation rate of the Ni (II) -EDTA is 30%, and the recovery rate of the cation deposited nickel can reach 10%.
Example 5
A treatment method of nickel ion-containing sewage comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photo-anode, a platinum electrode is a cathode, 10ppm nickel nitrate electrolyte is used for irradiating the photo-catalytic anode with 384nm ultraviolet light and is supplemented with2.1mA direct current, adjusting the pH value of the solution to 7 by using sulfuric acid and sodium hydroxide, electrolyzing for 120min, and obtaining the nickel ion removal rate of 90 percent.
Example 6
A treatment method of nickel ion-containing sewage comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photoanode, a platinum electrode is a cathode, 10ppm nickel nitrate electrolyte irradiates the photocatalytic anode with 384nm ultraviolet light and is supplemented with 2.8mA direct current, the pH value of the solution is adjusted to 7 by sulfuric acid and sodium hydroxide, electrolysis is carried out for 150min, and the removal rate of nickel ions can reach 92%.
Example 7
A treatment method of nickel ion-containing sewage comprises the following specific processes:
using the photocatalytic system setup as shown in FIG. 1, tiO deposition with FTO 2 The nanorod array is a photoanode, a platinum electrode is a cathode, 10ppm nickel nitrate electrolyte irradiates the photocatalytic anode with 384nm ultraviolet light and is supplemented with 1.4mA direct current, the pH value of the solution is adjusted to 7 by sulfuric acid and sodium hydroxide, electrolysis is carried out for 150min, and the removal rate of nickel ions can reach 81%.
Example 8
A method for recovering nickel ions comprises the following specific processes:
the nickel oxide attached to the photo-anode in the titanium dioxide nanorod array is used as a photocatalytic anode, a platinum electrode is used as a cathode, sodium sulfate is used as electrolyte, 384nm ultraviolet light is used for irradiating the photocatalytic anode, and-1 mA direct current is used for assisting, so that after 1min, all the nickel oxide attached to the photo-anode in the titanium dioxide nanorod array is released.
Example 9
A method for recovering nickel ions comprises the following specific processes:
the titanium dioxide nanorod array photoanode deposited with nickel oxide after the reaction of the embodiment 2 is placed in a reactor, and after 0.1M dilute sulfuric acid is added for reaction for 10min, all nickel oxide attached to the electrolysis of the titanium dioxide nanorod array photoanode is released and recovered.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A transition metal sewage treatment method is characterized by comprising the following steps:
under the conditions of light irradiation and electrification, treating the transition metal sewage by using a photocatalytic system comprising a photocatalytic anode, and depositing transition metal on the surface of the photocatalytic anode;
the photocatalytic anode comprises conductive glass loaded with a titanium dioxide nanorod array.
2. The transition metal wastewater treatment method according to claim 1, wherein the titanium loading of the photocatalytic anode is 12-20mg/cm 2 。
3. The method according to claim 1, wherein the transition metal wastewater contains at least one of free metal ions and/or complex metal ions of nickel, copper, manganese, and cobalt.
4. The method according to claim 3, wherein the pH of the transition metal-containing wastewater is 7 to 12.
5. The transition metal wastewater treatment method according to claim 3, wherein the complexing agent to which the complexed metal ions are bound comprises at least one of EDTA, phosphate, hydroxycarboxylic acid salt, and aminocarboxylic acid salt.
6. The method for treating transition metal wastewater according to claim 1, wherein the light irradiation is ultraviolet light.
7. According to the rightThe method for treating transition metal wastewater according to claim 1, wherein the energization is direct current; the current density of the direct current is 0.2mA/cm 2 -2.0mA/cm 2 。
8. The transition metal wastewater treatment method according to claim 1 or 2, wherein the preparation method of the photocatalytic anode comprises the following steps:
and placing the titanium source solution and the conductive glass into a reaction container, and carrying out hydrothermal reaction to obtain the photocatalytic anode.
9. The transition metal wastewater treatment method according to claim 8, wherein the hydrothermal reaction time is 4-6h.
10. A method for recovering a transition metal, comprising the steps of: after the transition metal wastewater treatment method according to any one of claims 1 to 9, the recovery of the transition metal is achieved by applying a reverse current or taking out the photoanode and placing the photoanode in an acid solution.
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