CN114835210B - Novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation - Google Patents

Novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation Download PDF

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CN114835210B
CN114835210B CN202210461270.7A CN202210461270A CN114835210B CN 114835210 B CN114835210 B CN 114835210B CN 202210461270 A CN202210461270 A CN 202210461270A CN 114835210 B CN114835210 B CN 114835210B
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cyanide
ultraviolet light
electrocatalytic
value
containing wastewater
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CN114835210A (en
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邹建平
王旭阳
殷梦英
田磊
滕成俊
郭先桂
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Nanchang Hangkong University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a novel method for treating cyanide by electrocatalytic coupling with ultraviolet light-assisted advanced oxidation, wherein the ultraviolet light combined with an electrocatalytic system can generate enough active chlorine species, and the pH value of the system is induced to be dynamically reduced, so that the hydrolysis of an intermediate product cyanate is effectively promoted, and the cyanide is selectively mineralized into nitrogen; the metal cyanide can be cracked under the irradiation of ultraviolet light to release free cyanide; then, free cyanide is rapidly oxidized to cyanate under the action of enough active chlorine species, so that the precipitation of HCN is effectively inhibited, in addition, the dynamic reduction of the pH value of a system effectively promotes the hydrolysis of an intermediate product cyanate to ammonia/ammonium salt, and finally, the active chlorine species selectively oxidize the ammonia/ammonium salt to nitrogen.

Description

Novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation.
Background
Cyanide has strong metal complexing ability and is often applied to industries such as metallurgy, coking, electroplating and the like, so that the cyanide exists in wastewater mainly in a metal complexing state. The metal cyanide can release highly toxic HCN under the acidic condition, and has serious harm to human bodies and ecology. The oxidation process is currently the most commonly used process for treating cyanide-containing wastewater (formulas 1-3). However, there is a great difference in the oxidation products of cyanide due to the difference in oxidation technology.
CN - +Oxidant→CNO - (1)
CNO - +2H 2 O→NH 3 +HCO 3 - (2)
NH 3 /NH 4 + +Oxidant→NO 3 - /N 2 (3)
Currently, most oxidation techniques treat cyanide-containing wastewater to produce the product Cyanate (CNO) - ). In order to prevent the formation of highly toxic HCN gas precipitation (pKa (HCN/CN) - ) =9.21), it is necessary to keep the treatment system under strongly alkaline conditions. The cyanate produced is a weak acid salt, and can inhibit hydrolysis under the condition of strong alkali, so that cyanide can only be oxidized to low-toxicity cyanate in the treatment technology. Nitrate is an ideal and non-toxic product of cyanide oxidation processes compared to cyanate. However, limited by the recalcitrance of cyanate under alkaline conditions and the large energy input required for ammoxidation after hydrolysis, few techniques have been available to achieve deep oxidation of cyanide to nitrate. Recently, the innovation of the subject group provides an electro-Fenton system which can effectively overcome the difficulties existing in the deep oxidation process of cyanide. By in situ generation in the electro-Fenton system · OH and · O 2 - the cyanide can be efficiently converted into nontoxic nitrate in an electro-Fenton system under the synergistic effect, and the generation of low-toxicity intermediate product cyanate is avoided. However, nitrate is not the cyanide conversion product and nitrogen is the most desirable product in cyanide oxidation processes due to the stringent total nitrogen standards present for wastewater discharge. Limited to cyanate hydrolysis and ammonia selective oxidation, only the photoelectrocatalytic system (PEC) proposed by Koo et al currently enables conversion of cyanide to nitrogen. By virtue of the property of cyanate salts that hydrolyze to ammonia at pH values below 10, they adjust the PEC system pH values in the range of 9.21 to 10. Subsequently, conversion of cyanide with nitrogen is initially achieved in combination with the generation of active chlorine species on the photoanode. However, when the initial pH is within this narrow range, the hydrolysis rate of the intermediate cyanate is very slow and the reactivity of the active chlorine species is also severely inhibited. Therefore, the conversion efficiency between cyanide and nitrogen is extremely low, making such PEC systems unsuitable for practical processes. Therefore, in order to achieve the effective conversion of cyanide into nitrogen, it is highly desirable to develop an efficient and convenient processThe process solves the problems of cyanate hydrolysis and ammonia selective oxidation into nitrogen in the cyanide-containing wastewater treatment process.
Therefore, the invention constructs an ultraviolet light combined electro-catalytic system, which effectively promotes the hydrolysis of cyanate and selectively oxidizes ammonia into nitrogen, and further realizes the mineralization of cyanide. Wherein the metal cyanide dissociates under ultraviolet light irradiation, releasing the free cyanide ligand. Meanwhile, the addition of Persulfate (PS) as a precursor can promote the formation of active species, induce the reduction of the pH value of the reaction solution and further promote the hydrolysis of cyanate. In addition, the electrocatalytic process can form active chlorine species, which are more reactive as the pH decreases, and can selectively oxidize cyanide efficiently to nitrogen. The generation of enough active species in the system ensures that cyanide is oxidized rapidly, does not accumulate to the saturated concentration under the low pH value, and effectively inhibits the precipitation of HCN under the low pH value.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows: the new method for treating cyanide by electrocatalytic coupling with ultraviolet light assisted advanced oxidation comprises the following steps of firstly, adding a certain amount of persulfate into cyanide-containing wastewater, and regulating and controlling the pH value in the cyanide-containing wastewater to a preset value; then, treating cyanide-containing wastewater by using an ultraviolet light combined with an electrocatalytic system; by regulating the initial current density, introducing enough active chlorine species to enable free cyanide generated after metal cyanide in cyanide-containing wastewater breaks down the collaterals to be immediately converted into low-toxicity cyanate; and the interconversion between the active chlorine species is capable of inducing a pH value of 1.1X10 in cyanide-containing wastewater -2 min -1 The rate of the reaction is moderately self-reduced, so that a strict matching relation is formed between the pH value self-reduction rate and the oxidation capacity in cyanide-containing wastewater, thereby reducing the pH value of a system and promoting the hydrolysis of an intermediate product cyanate under the condition of no formation of HCN; strong oxygen re-binding active chlorine speciesThe chemical capacity, and finally the cyanide in the cyanide-containing wastewater is oxidized into nitrogen with high selectivity.
Preferably, the anode material in the ultraviolet light combined electrocatalytic system is commercial stable anode or cobaltosic oxide, the cathode material is carbon material, the electrolyte solution is sodium chloride solution, the electrochemical workstation provides constant current, and the 300W xenon lamp provides ultraviolet light source irradiation.
Preferably, the pH value regulating liquid used for regulating the pH value in the wastewater to a preset value is sodium hydroxide solution, and the persulfate is potassium persulfate or sodium persulfate.
Preferably, the reaction device used by the ultraviolet light combined with the electrocatalytic system is a quartz photoelectric reactor with the volume of 150mL or 250mL, and the ultraviolet irradiation and electrochemical residence time is 120-360min.
The invention has the beneficial effects that:
the ultraviolet light combined with the electrocatalytic system can effectively promote the speed limiting step in the traditional cyanide conversion process, and can efficiently convert cyanide into an ideal nitrogen product. In addition, the reasonable selection of the reaction conditions of the system can effectively realize the efficient mineralization of cyanide and strictly inhibit the precipitation of highly toxic HCN. Effectively solves the contradictory relation in the traditional cyanide conversion process, and opens up a new safe and efficient complete cyanide detoxification method.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention.
FIG. 1 is a schematic diagram of an electrocatalytically coupled ultraviolet light-assisted advanced oxidative deep mineralization metal cyanide of the present invention;
FIG. 2 is a graph showing the performance of the electrocatalytic coupling ultraviolet assisted advanced oxidation treatment cyanide at different initial pH values in accordance with the present invention;
FIG. 3 is a graph showing the pH change during cyanide mineralization at various initial pH values in accordance with the present invention;
FIG. 4 is a graph showing the performance of electrocatalytic coupling ultraviolet assisted advanced oxidation treatment cyanide at different PS additions in accordance with the present invention;
FIG. 5 is a graph showing the pH change during cyanide mineralization at various PS additions in accordance with the present invention;
FIG. 6 is a graph of the performance of electrocatalytically coupled UV-assisted advanced oxidation treatment cyanide at different current densities in accordance with the present invention;
FIG. 7 is a graph showing the pH change during cyanide mineralization at the same current density in accordance with the present invention;
FIG. 8 is a graph showing the time profile of iron ions, free cyanide, total cyanide and total nitrogen in the system of the present invention;
FIG. 9 is a graph showing the time profile of cyanate, ammonia, nitrate and nitrite in the system according to the present invention;
FIG. 10 is a graph of active species capture experiments during cyanide oxidation in an electrocatalytically coupled UV-assisted advanced oxidation system according to the present invention;
FIG. 11 is a graph of an active species capture experiment during total nitrogen removal in an electrocatalytically coupled UV-assisted advanced oxidation system according to the present invention;
FIG. 12 is an EPR spectrum of the electrocatalytically coupled ultraviolet assisted advanced oxidation system of the present invention;
FIG. 13 is a graph showing steady state concentrations of different active species of the electrocatalytically coupled UV-assisted advanced oxidation system of the present invention.
Detailed Description
Reference will now be made in detail to the present embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein the accompanying drawings are used to supplement the description of the written description so that one can intuitively and intuitively understand each technical feature and overall technical scheme of the present invention, but not to limit the scope of the present invention.
Referring to fig. 1-13, a novel method for treating cyanide by electrocatalytically coupling ultraviolet light-assisted advanced oxidation according to a preferred embodiment of the present invention comprises the steps of firstly adding a certain amount of persulfate to selected cyanide-containing wastewater, and regulating the pH value of the cyanide-containing wastewater to a preset value; then, treating cyanide-containing wastewater by using an ultraviolet light combined with an electrocatalytic system; introduction of foot by controlling initial current densityThe amount of active chlorine species is such that free cyanide generated after the metal cyanide in cyanide-containing wastewater breaks down the complex is immediately converted into low-toxicity cyanate; the common complex cyanide in cyanide-containing wastewater is ferricyanide, cobalt cyanide, copper cyanide and the like; and the interconversion between the active chlorine species is capable of inducing a pH value of 1.1X10 in cyanide-containing wastewater -2 min -1 The rate of the waste water is moderately self-reduced, so that a strict matching relation is formed between the pH value self-reduction rate and the oxidation capacity in the waste water, the pH value of cyanide-containing waste water is reduced under the condition of no HCN formation, and the hydrolysis of an intermediate product cyanate is promoted; and finally, the cyanide in the cyanide-containing wastewater is oxidized into nitrogen with high selectivity by combining the strong oxidizing capability of the active chlorine species.
The addition of the persulfate as a precursor not only can promote the formation of active chlorine species, but also can induce the reduction of the pH value of the reaction solution to further promote the hydrolysis of cyanate. In addition, the electrocatalytic process combined with persulfate can form active chlorine substances, and the active chlorine substances are more reactive with the decrease of the pH value, so that cyanide can be selectively and effectively oxidized into nitrogen; the ultraviolet light is combined with the generation of enough active chlorine species in the electrocatalytic system, so that cyanide is rapidly oxidized, the cyanide cannot be accumulated to a saturated concentration at a low pH value, and the precipitation of HCN is effectively inhibited.
As a preferred embodiment of the invention, it may also have the following additional technical features:
in this embodiment, the anode material in the ultraviolet light combined electrocatalytic system is commercial stable anode or cobaltosic oxide, the cathode material is carbon material, the electrolyte solution is sodium chloride solution, the electrochemical workstation provides constant current, and the current density is 2-20mA/cm 2 Irradiating with 300W xenon lamp to obtain ultraviolet light source, inserting two electrodes into electrolyte solution before reaction, soaking with a soaking area of 4.5cm 2 And is fixed at the gap of 4cm of the electrode clip.
In the embodiment, the pH value regulating solution used for regulating the pH value in the wastewater to a preset value is a sodium hydroxide solution, 50mM NaCl is added for regulating the conductivity, and the persulfate is potassium persulfate or sodium persulfate, and the dosage is 1-5mM.
In the embodiment, the reaction device used by combining the ultraviolet light with the electrocatalytic system is a quartz photoelectric reactor with the volume of 150mL or 250mL, the ultraviolet light irradiates from the position of 2cm away from the left side of the photoelectric reactor, and the ultraviolet irradiation and electrochemical residence time is 120-360min.
In the reaction process, the photoelectric reactor is completely sealed, a plastic pipe is used for connecting with an absorption solution, preferably, naOH with the concentration of 1M, and HCN is collected; after the reaction is finished, air is slowly blown into the absorption solution for 30min so as to completely absorb the residual escaped HCN in the reactor; the cyanide mineralization experiments were repeated in an open system without HCN precipitation.
Example 1 treatment of ferricyanide common in actual cyanide-containing wastewater of the present invention
In the embodiment of the invention, ferricyanide common in the actual cyanide-containing wastewater is used as a treatment object. First, a certain amount of 0.25mM potassium ferricyanide solution is added into a photoelectric reactor; adjusting the pH value to a preset value by using NaOH solution, adding 50mM sodium chloride into a beaker, stirring and dissolving, and pouring the solution into a reactor; adding a certain amount of persulfate solid into the reactor, and stirring to completely dissolve the persulfate solid; taking a commercial stable electrode as an anode and active carbon fiber as a cathode, and preheating a full spectrum xenon lamp for 20min in advance; sealing and reacting for 2 hours under the irradiation of a certain current density and an ultraviolet lamp; the HCN which may precipitate is absorbed by catheterization in 0.1M sodium hydroxide solution using a plastic catheter; after ensuring no HCN precipitation, the above experiments were repeated and each sample was taken at the set time node using a 5mL syringe, each sample being 2mL, filtered through a 0.22 μm filter head and placed in a 5mL centrifuge tube.
The specific preparation method of the electrode material in this example is as follows:
the specific preparation method of the cathode electrode material activated carbon fiber comprises the following steps: firstly, cutting activated carbon fibers to a size of 1.5cm multiplied by 4 cm; immersing the cut activated carbon fiber into 3M nitric acid solution for activation for 13h, washing the activated carbon fiber to be neutral by a large amount of deionized water, and then drying and sealing the activated carbon fiber for standby.
Example 2 treatment of cobalt cyanide common in actual cyanide-containing wastewater of the invention
In the embodiment of the invention, common cobalt cyanide in actual cyanide-containing wastewater is used as a treatment object; first, a certain amount of 0.25mM potassium cobalt cyanide solution is added into a photoelectric reactor; adjusting the pH value to a preset value by using NaOH solution, adding 50mM sodium chloride into a beaker, stirring and dissolving, and pouring the solution into a reactor; adding a certain amount of persulfate solid into the reactor, and stirring to completely dissolve the persulfate solid; taking cobaltosic oxide as an anode and a carbon felt as a cathode, and preheating a full-spectrum xenon lamp for 20min in advance; sealing and reacting for 2 hours under the irradiation of a certain current density and an ultraviolet lamp; the HCN which may precipitate is absorbed by catheterization in 0.1M sodium hydroxide solution using a plastic catheter; after ensuring no HCN precipitation, the above experiments were repeated and each sample was taken at the set time node using a 5mL syringe, each sample being 2mL, filtered through a 0.22 μm filter head and placed in a 5mL centrifuge tube.
The specific method for preparing the electrode material and the solution in this example is as follows:
the specific preparation method of the cathode electrode material cobaltosic oxide comprises the following steps: firstly, respectively ultrasonically cleaning an FTO substrate of 1.5cm multiplied by 4cm by using acetone, ethanol and ultrapure water for 10min, and drying for later use; then 0.582g of cobalt nitrate is dissolved in 10mL of glycol and 30mL of water, 0.5g of urea, 1.455g of ammonium fluoride and 0.05g of polyvinylpyrrolidone are sequentially added into the above solution, the mixture is stirred for 30min at room temperature, and the uniformly mixed solution is transferred into a 100mL reaction kettle; finally, immersing a processed FTO substrate into the reaction solution in an inclined way; the autoclave was sealed and reacted at 120 ℃ for 12h; after the reaction was completed, the electrode was washed with a large amount of deionized water and dried at 60 ℃. Calcining the dried electrode material in air, maintaining the temperature at 350 ℃ for 2 hours, and then raising the temperature to 550 ℃ and maintaining the temperature for 2 hours; cooling to room temperature for standby.
The specific preparation method of the cathode electrode material carbon felt comprises the following steps: firstly, cutting a carbon felt to a size of 1.5cm multiplied by 4 cm; immersing the cut carbon felt into 3M nitric acid solution for activation for 13h, washing the carbon felt to be neutral by a large amount of deionized water, and then drying and sealing the carbon felt for standby.
The complete detoxification effect of the present invention on cyanide and its mechanism of action are discussed in detail by the specific experimental results of inventive example 1.
As shown in fig. 2-7, cyanide can be efficiently converted to nitrogen in an ultraviolet light combined with an electrocatalytic system; the mineralization rate of cyanide is mainly influenced by the initial pH value, the addition amount of persulfate and the current density. Furthermore, the pH change during cyanide-combined mineralization is known to be dynamic in the uv-combined electrocatalytic system, which also leads to HCN precipitation under extreme conditions; through experimental condition regulation, the initial pH value is 11.50, the adding amount of persulfate is 3mM, and the current density is 20mA/cm 2 In the case of (2), ferricyanide can be fully mineralized into nitrogen in the ultraviolet light combined with the electrocatalytic system, and HCN is not precipitated.
The change in concentration of each species during cyanide conversion was measured. As shown in fig. 8-9, the concentration of FCN in the uv-binding electrocatalytic system was always approaching 0 during the reaction, indicating that no free cyanide was accumulated in the uv-binding electrocatalytic system. Therefore, a decrease in pH does not lead to the formation of HCN. As the reaction proceeds, the concentrations of iron ions, total cyanide and total nitrogen gradually decrease, and gradually decrease below zero. Since the previous closed system did not exhibit HCN leakage, the decrease in total nitrogen concentration was attributed to the generation of nitrogen. In addition, the concentration of cyanate is increased and then decreased during the reaction. The dynamic reduction of the pH value in the ultraviolet light combined with the electrocatalytic system is beneficial to the rapid hydrolysis and further conversion of cyanate; ammonia is selectively oxidized to nitrogen due to the large amount of active chlorine species generated during the electrocatalytic process.
FIGS. 10-13 show the determination of ClO by quenching experiments, EPR tests and determination of steady state concentration of free radicals for active chlorine species in UV light combined with an electrocatalytic system · And Cl 2 ·- Is the main active species in cyanide mineralization, and can selectively oxidize cyanide to nitrogen.
As can be seen from the above embodiments: the invention realizes deep mineralization detoxification from cyanide to nitrogen by constructing a novel ultraviolet light combined electrocatalytic system. The pH value of the system is induced to self-reduce by optimizing the initial pH value, the addition amount of persulfate and the current density in the system, and simultaneously promoting the generation of enough active chlorine species, thereby promoting the speed limiting step (cyanate hydrolysis) in the traditional cyanide conversion process. Subsequently, the cyanide is mineralized to nitrogen with high efficiency in combination with the high selectivity of the active chlorine species to ammonia oxidation. In addition, due to the existence of enough active species, cyanide monomers after the channel breaking are promoted not to accumulate to the saturated concentration, so that the precipitation of HCN under the low pH value is inhibited. The ultraviolet light combined with the electrocatalytic system can effectively promote the hydrolysis of low-toxicity product cyanate, promote the speed limiting step in the traditional cyanide detoxification process, selectively oxidize cyanide to nitrogen, and simultaneously inhibit the precipitation of HCN, thereby having great application prospect in the field of actual cyanide-containing wastewater treatment.
The ultraviolet light combined with the electrocatalytic system can effectively promote the speed limiting step in the traditional cyanide conversion process, and can efficiently convert cyanide into an ideal nitrogen product. In addition, the reasonable selection of the reaction conditions of the system can effectively realize the efficient mineralization of cyanide and strictly inhibit the precipitation of highly toxic HCN. Effectively solves the contradictory relation in the traditional cyanide conversion process, and opens up a new safe and efficient complete cyanide detoxification method.
Specifically, the specific determination method for the content of each product in the invention is as follows:
the change in total nitrogen concentration was measured using a conventional alkaline persulfate oxidation method.
And measuring the concentration change of ammonia nitrogen in the reaction system by adopting a Nahner reagent spectrophotometry. The spectrophotometer model used was U-3900,Hitachi Ltd,Japan.
The concentration change of active chlorine was measured by DPD spectrophotometry. The spectrophotometer model used was U-3900,Hitachi Ltd,Japan.
And determining the concentration change of the total cyanide and the free cyanide in the reaction system by adopting an isonicotinic acid-barbituric acid colorimetric method.
And measuring the content change of cyanate, nitrite and nitrate in the reaction system by adopting an ion chromatography. The ion chromatograph used was Dionex-120,Dionex Inc,USA.
The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.
The foregoing is only a preferred embodiment of the present invention, and all technical solutions for achieving the object of the present invention by substantially the same means are within the scope of the present invention.

Claims (3)

1. A novel method for treating cyanide by electrocatalytic coupling ultraviolet light assisted advanced oxidation is characterized by comprising the following steps: firstly, adding 3mM persulfate into cyanide-containing wastewater, and regulating the pH value of the cyanide-containing wastewater to 11.50; then, treating cyanide-containing wastewater by using an ultraviolet light combined with an electrocatalytic system; by controlling the initial current density to be 20mA/cm 2 The anode material in the ultraviolet light combined electrocatalytic system is commercial stable anode or cobaltosic oxide, the cathode material is carbon material, the electrolyte solution is 50mM sodium chloride solution, the electrochemical workstation provides constant current, the 300W xenon lamp provides ultraviolet light source irradiation to obtain active chlorine species, and the active chlorine species is ClO • And Cl 2 •- The free cyanide generated after the metal cyanide in the cyanide-containing wastewater is broken is immediately converted into low-toxicity cyanate; and the interconversion between the active chlorine species is capable of inducing a pH value of 1.1X10 in cyanide-containing wastewater -2 min -1 The rate of the reaction is moderately self-reduced, so that a strict matching relation is formed between the pH value self-reduction rate and the oxidation capacity in cyanide-containing wastewater, thereby reducing the pH value of a system and promoting the hydrolysis of an intermediate product cyanate under the condition of no formation of HCN; and finally, the cyanide in the cyanide-containing wastewater is oxidized into nitrogen with high selectivity by combining the strong oxidizing capability of the active chlorine species.
2. The novel electrocatalytic coupling ultraviolet light assisted advanced oxidation cyanide treatment method as set forth in claim 1, wherein: the pH value regulating liquid used for regulating the pH value in the wastewater to 11.50 is sodium hydroxide solution, and the persulfate is potassium persulfate or sodium persulfate.
3. The novel electrocatalytic coupling ultraviolet light assisted advanced oxidation cyanide treatment method as set forth in claim 1, wherein: the reaction device used by combining the ultraviolet light with the electrocatalytic system is a quartz photoelectric reactor with the volume of 150mL or 250mL, and the ultraviolet irradiation and electrochemical residence time is 120-360min.
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