CN113461234A - Method and equipment for electrochemically treating industrial wastewater by using medium-frequency power supply - Google Patents
Method and equipment for electrochemically treating industrial wastewater by using medium-frequency power supply Download PDFInfo
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Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention provides a method and a device for electrochemically treating industrial wastewater by using a medium-frequency power supply, which comprises three parts: a medium frequency power supply, an electrode assembly, an electrolytic cell, and an electrochemical process for treating wastewater. Specifically, the electrodes are placed in an electrolytic cell, wastewater enters from one end of the electrolytic cell, and flows out from the other end of the electrolytic cell. When the electrolytic cell runs, the medium-frequency power supply is turned on, the anode electrode starts to oxidize and degrade organic matters, and after the electrolytic cell runs for a period of time, the wastewater meets the discharge requirement. The adoption of the medium-frequency power supply can reduce the diffusion mass transfer resistance, effectively inhibit the passivation corrosion of the electrode and prolong the service life of the electrode. Meanwhile, the electrode can effectively play the role of the electrode when the electrode operates at low voltage, thereby reducing the energy consumption. Electrodes in the medium-frequency power supply electrooxidation mode are mutually cathodes and anodes, the problem of cathode scaling in the traditional electrooxidation process is avoided, and therefore the reduction of the electrode efficiency is delayed and the equipment maintenance period is shortened. Because the medium-frequency power supply adopts sine wave current output, the electrode always runs in a high-efficiency area, and the oxidation efficiency of the electrolytic cell is improved.
Description
Technical Field
The invention relates to the technical field of energy conservation and environmental protection, in particular to a method and equipment for electrochemically treating industrial wastewater by using a medium-frequency power supply.
Background
Industrial wastewater has complex components, is difficult to treat and has great potential harm to the environment, and no good single method for treating the wastewater exists so far. The traditional physical and chemical method cannot effectively remove organic compounds which are difficult to degrade in industrial wastewater, only can remove a part of pollution factors under normal conditions, and can cause secondary pollution. With the stricter and stricter requirements on zero emission and the requirement on resource utilization, the advanced oxidation technology is generally concerned because of no secondary pollution and good removal effect.
Ozone is a typical representative technology in the advanced oxidation technology and is a relatively universal technology, but the treatment effect is poor, the investment and operation cost is high, the market reaction is not good, so the application is also greatly limited, the electrochemical technology is a relatively widely applied technology and has the same superiority as the ozone technology, but the traditional electrochemical technology has the problems of cathode pollution, diffusion and serious anode passivation, the anode service life is short due to long-term high-potential operation, and the treatment effect is general. Patent CN103086449A, the intermediate frequency power supply is used for electric heating system, concentrate waste water, produce steam and dense water, compress to steam and produce condensation behind the high pressure steam electricity generation, dense water gets into the filter-pressing behind the sludge impoundment, the evaporation energy consumption is high, the secondary steam compression is recycled inefficiency, there is low boiling point component steam in the waste water steam simultaneously, also be noncondensable gas, unfavorable to power generation system, the concentrated water that produces simultaneously, if contain salt too high, the filter-pressing becomes the mud cake after the method is stored at the sludge impoundment at all. Completely different from the present invention. Therefore, there is a need for a more optimized electrochemical wastewater treatment method to solve the above problems.
Disclosure of Invention
In view of the above, the present invention provides a method for electrochemically treating industrial wastewater by using an intermediate frequency power supply, and mainly aims to improve the adaptability of the electrochemical technology in industrial wastewater treatment so as to expand the effect of electrochemistry in environmental treatment. Due to cathode scaling and anode concentration diffusion limitation, anode voltage is increased and water decomposition is severe in the traditional electrochemistry, so that the service life of a coating is short, the energy consumption is high, the treatment effect is poor, and the market application is greatly limited. The intermediate frequency power supply electrochemical technology, the electrodes are the negative and positive electrodes each other, the problem of anode voltage rise caused by the limitation of cathode structure and anode concentration diffusion is effectively overcome, the service life of the electrodes is prolonged, the energy consumption is reduced, and a better removal effect is achieved. The invention overcomes the problem of cathode pollution, effectively solves the problems of mass transfer, and the like, and simultaneously reduces the problem that the service life is influenced by the continuous action of current on the polar plate, thereby solving the problem of high energy consumption. In order to achieve the purpose, the invention mainly provides the following technical scheme:
an apparatus for electrochemical treatment of industrial wastewater by a medium frequency power supply, comprising:
the medium-frequency power supply is used for providing a power supply required by electrochemical treatment of industrial wastewater;
the electrode assembly is used for degrading organic matters in the wastewater through electrochemical reaction;
the electrolytic tank is internally provided with a reaction area for electrochemical reaction of wastewater, one side of the tank body is provided with a wastewater inlet, and the other side of the tank body is provided with a wastewater outlet;
the post oxidation device is arranged behind the electrolytic bath and is used for further oxidizing the wastewater;
the pretreatment device is used for pretreating the pretreated industrial wastewater;
and the circulating pump is arranged between the pretreatment device and the electrolytic bath and is used for conveying the wastewater after pretreatment to the electrolytic bath.
Furthermore, the current output of the intermediate frequency power supply is a sinusoidal curve, the frequency is 400Hz-10KHz, and preferably, the frequency is 500Hz-5 KHz; voltage less than 10V and current 200A/m2-3000A/m2Preferably 800A/m2-2500A/m2。
Furthermore, the electrode of the electrode assembly is graphite and PbO2One or a combination of more of ruthenium oxide, iridium oxide, ruthenium iridium oxide, doped ruthenium iridium oxide, Pt, Au, BDD and tin antimony oxide; the shape of the electrode is tubular, reticular or plate-shaped, and the electrodes are combined into one or more groups, preferably, circular reticular. The cathode and the anode of the electrode can be similar electrodes or different electrodes, and are preferably ruthenium oxide, iridium oxide, ruthenium iridium oxide and doped metal oxide coating electrodes thereof, noble metal electrodes and BDD electrodes in the working process.
Furthermore, the cathode and the anode of the electrode are both net-shaped and adopt a sleeve structure.
Furthermore, the electrolytic cell is corrosion-resistant, oxidation-resistant and ultraviolet-resistant, and is made of one of PP, PVC, UPVC, FRP, PVDF, glass fiber reinforced plastic, stainless steel, dual-phase steel, titanium material and steel lining plastic.
The invention also provides a method for electrochemically treating process wastewater by using the medium-frequency power supply, and the equipment for electrochemically treating industrial wastewater by using the medium-frequency power supply comprises the following steps:
(1) assembling electrodes in a reaction zone: selecting the length, area and number of groups of electrodes as required, wherein the distance between the cathode plate and the anode plate is 0.5-3cm, adopting a mesh sleeve, the number of the electrodes in series connection is less than 10, and selecting the number of groups in parallel connection as required; preferably, the distance between the polar plates is 1-1.5cm, the outer tube is 5-7cm, and 5-10 electrodes are connected in series;
(2) pretreating the wastewater by a pretreatment device: removing hard substances of calcium, magnesium and silicon in the wastewater and suspended substances polluting the surface of the electrode so as to reduce the problems of performance and service life attenuation caused by electrode damage caused by voltage rise due to unnecessary factors;
(3) the pretreated wastewater enters from the bottom inlet of the electrolytic cell through a circulating pump, passes through a buffer zone and overflows to a catalytic oxidation reaction zone;
(4) and (3) post-oxidation process stage: the wastewater overflows to a post oxidation device for post oxidation treatment after passing through an electrolytic reaction zone;
(5) turning on the intermediate frequency power supply, setting the frequency of 500Hz-5KHz and the current of 800A/m2-2500A/m2And (3) oxidizing and degrading organic matters by the anode electrode, reacting for 10-120min, and discharging the sewage after the sewage reaches the standard.
Furthermore, the post-oxidation treatment stage can supplement hydrogen peroxide, or ultraviolet light, or an ultraviolet light plus catalytic system, preferably, active substances are generated after ultraviolet light activation electrocatalysis is adopted, or ultraviolet light is cooperated with an immobilized catalyst.
Further, activating substances are catalytically excited by ultraviolet light, the ultraviolet light is inserted into the quartz sleeve and then is inserted into wastewater, the ultraviolet light can be arranged in series or in parallel according to the requirement, the synergistic efficiency of the ultraviolet light is improved, the outer wall of the quartz sleeve is coated by colloid, then the high-temperature treatment is carried out, the colloid component is one or more of tungsten, molybdenum, iron and cerium doped nano titanium dioxide, the doping amount is less than 10%, and the preferred weight ratio is 0.1-3%.
And further, before the wastewater enters the buffer area, the hardness and the suspended matters are pretreated to reduce the influence of the hardness on the service life of the electrode, and after the wastewater is pretreated, the pH value of the wastewater is preferably adjusted to be in a range of 3-7.
Compared with the prior art, the method for electrochemically treating industrial wastewater by using the medium-frequency power supply has the following beneficial effects that:
the conventional electrochemical technology has the defects of short anode service life, high energy consumption, poor industrial wastewater treatment effect and the like, and the main reason is that only the anode problem is generally concerned, in fact, although the anode participates in the oxidation reaction, the performance of the cathode on the whole electrochemical system is seriously influenced, the voltage of a tank is increased due to scaling of the cathode, and the phenomenon that the anode decomposes water or oxidizes electrolyte is aggravated due to mass transfer influence, so that the active ingredients of the anode are dissolved, the service life of the electrode is prolonged, and the treatment effect is reduced. The electrochemical treatment of industrial waste water by using a medium-frequency power supply. Firstly, a medium-frequency power supply outputs sine wave current and positive and negative pulse current, electrodes are mutually a cathode and an anode, and compared with an electrooxidation mode under the action of continuous anode current, the treatment performance can be ensured, the damage of voltage rise to the anode caused by concentration diffusion mass transfer can be reduced, and the energy consumption can be reduced; secondly, through polarity conversion, the two polar plates are mutually a cathode and an anode, so that the influence of cathode scaling on the whole electrochemical system is effectively inhibited, the influence of diffusion on a single anode can be reduced, and the influence of mass transfer is effectively reduced; thirdly, compared with a pulse power supply, the electrode always works in a high-efficiency area, and the electrolysis efficiency is higher; fourthly, the influence of the pollution on the surface of the electrode on the electrochemical treatment of industrial wastewater is effectively inhibited by controlling the hardness indexes of water inlet indexes such as calcium, magnesium and silicon and the pH value of the inlet water, the coupling photocatalysis process strengthens and utilizes the substances which are generated by electrochemistry and have low energy and are not enough to continuously oxidize the pollutants which are difficult to degrade, and the stability and the applicability of the electrochemistry are improved.
Drawings
FIG. 1 is a schematic diagram of a structure of intermediate-frequency electrochemical treatment of industrial wastewater
In the figure: 1. a medium frequency power supply; 2. an electrode; 3. an electrolytic cell; 4. a circulation pump; 5. waste water; 6. a post oxidation device; 7. an interface of the pretreatment device.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the intended purpose, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments
In one aspect, an embodiment of the present invention provides an apparatus for electrochemically treating industrial wastewater by using a medium-frequency power supply, including:
the medium-frequency power supply is used for providing a power supply required by electrochemical treatment of industrial wastewater, the current output is a sine curve, the frequency is 400Hz-10KHz, and preferably, the frequency is 500Hz-5 KHz; voltage less than 10V and current 200A/m2-3000A/m2Preferably 800A/m2-2500A/m2(ii) a In order to achieve the optimal operating conditions, the current parameter selection is determined according to the redox current of the pollution factors in the wastewater;
the electrode assembly is used for degrading organic matters in the wastewater through electrochemical reaction; wherein the electrode is graphite, PbO2One or a combination of more of ruthenium oxide, iridium oxide, ruthenium iridium oxide, doped ruthenium iridium oxide, Pt, Au, BDD and tin antimony oxide; the electrodes are tubular, net-shaped and plate-shaped, and are combined into one or more groups, preferably circular net-shaped; the cathode and the anode of the electrode can be similar electrodes or different electrodes, and are mutually cathode and anode in the working process, preferably ruthenium oxide, iridium oxide, ruthenium iridium oxide and doped metal oxide coating electrodes thereof, noble metal electrodes and BDD electrodes; the cathode and the anode are both net-shaped and adopt a sleeve structure;
the electrolytic bath is internally provided with a reaction area for electrochemical reaction of wastewater, one side of the bath body is provided with a wastewater inlet, and the other side of the bath body is provided with a wastewater outlet, and the electrolytic bath is corrosion-resistant, oxidation-resistant and ultraviolet-resistant and is made of one of PP, PVC, UPVC, FRP, PVDF, glass fiber reinforced plastic, stainless steel, dual-phase steel, titanium material and steel lining plastic;
the post oxidation device is arranged behind the electrolytic bath and is used for further oxidizing the wastewater;
the pretreatment device is used for pretreating the pretreated industrial wastewater;
and the circulating pump is arranged between the pretreatment device and the electrolytic bath and is used for conveying the wastewater after pretreatment to the electrolytic bath.
The specific equipment connection is as follows: the electrodes 2 are arranged in the electrolytic tank 3 after being assembled, the intermediate frequency power supply 1 is arranged at two ends of the electrodes to provide electrochemical power supply, the leading-in port of the electrolytic tank 3 is connected with the circulating pump 4, the circulating pump 4 can be connected with the interface 7 of the pretreatment device in the electrolytic tank 3 for conveying pretreated waste water, so as to be connected with the pretreatment device of the waste water, the leading-out port of the electrolytic tank is connected with the post-oxidation device, and the waste water 5 is filled in the electrolytic tank 3 and the post-oxidation device 6.
In another aspect, an embodiment of the present invention further provides a method for electrochemically treating industrial wastewater by using a medium-frequency power supply, wherein the method includes the following steps:
(1) assembling electrodes in a reaction zone: selecting the length, area and number of groups of electrodes as required, wherein the distance between the cathode plate and the anode plate is 0.5-3cm, adopting a mesh sleeve, the number of the electrodes in series connection is less than 10, and selecting the number of groups in parallel connection as required; preferably, the distance between the polar plates is 1-1.5cm, the outer tube is 5-7cm, and 5-10 electrodes are connected in series;
(2) pretreating the wastewater by a pretreatment device: the conventional wastewater treatment device is adopted to remove hardness substances such as calcium, magnesium, silicon and the like in wastewater and substances such as suspended matters polluting the surface of an electrode so as to reduce the problems of performance and service life attenuation caused by electrode damage caused by voltage rise due to unnecessary factors; carrying out electrochemical test on the wastewater to know the oxidation-reduction current of pollution factors in the wastewater so as to reduce unnecessary energy consumption and damage of inappropriate operating parameters to electrodes; in order to further control the stability of the system and prevent the problem of incomplete pretreatment pollution to the electrode system, the pH value of the wastewater is adjusted to 3-7;
(3) the pretreated wastewater enters from the bottom inlet of the electrolytic cell through a circulating pump, passes through a buffer zone and overflows to a catalytic oxidation reaction zone,
(4) and (3) post-oxidation process stage: the wastewater overflows to a post-oxidation device for post-oxidation treatment after passing through an electrolytic reaction zone, part of species in active substances generated by electrochemistry can not be consumed immediately, and the oxidation energy of the active substances entering the post-oxidation zone is not enough to continuously oxidize nondegradable pollution factors, couple an oxidant or provide energy to further improve the oxidation capacity of the active substances; preferably, ultraviolet light is adopted to catalyze and excite active substances, the ultraviolet light is inserted into the quartz sleeve and then is inserted into the wastewater, the quantity is configured according to the requirement, the ultraviolet light can be connected in series or in parallel, the synergistic efficiency of the ultraviolet light is improved, the outer wall of the quartz tube is coated by colloid, then the high-temperature treatment is carried out, the colloid component is one or more of tungsten, molybdenum, iron and cerium, the doping amount is less than 10%, and preferably, the weight ratio is 0.1-3%;
(5) turning on the intermediate frequency power supply, setting the frequency of 500Hz-5KHz and the current of 800A/m2-2500A/m2The retention time is 10-120 min; and discharging the sewage after reaching the standard.
The specific embodiment is as follows:
example 1
Perfluorooctanoic acid wastewater, wherein the TOC of raw water is 735mg/L, the raw water is light yellow, the content of chloride ions is 24800mg/L, the total hardness is 187mg/L, the pH is adjusted to 3.5, the hardness is removed by a double-alkali method (a common hardness removal method is mainly sodium carbonate and sodium hydroxide), the hardness after removal is 31mg/L, and the pH is adjusted back to 6.0; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water; assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the intermediate frequency power supply, setting the frequency at 1200Hz and the current at 920A/m2The initial voltage is 5.9V, the retention time is 30min, and the test is started;
post oxidation stage, 5% TiO2Colloid, doped cerium 0.5 wt% and iron 0.1 wt% (iron, cerium)The amount of (A) is relative to the amount of TiO2Amount of the ultraviolet lamp tube, the ultraviolet lamp tube with the wavelength of 254nm is inserted into the quartz tube after being coated on the quartz tube and baked for 1 hour at 500 ℃, the stay time is about 30min according to the arrangement results of one group of 5 tubes and three groups after being sealed, and the experiment is started;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 16mg/L, the effluent is detected by a spectrophotometer, no perfluorooctanoic acid signal exists in an ultraviolet region, and after one week of continuous operation, the average electrochemical energy consumption is 4.6Kwh/m3The voltage is 6.2V;
example 2
Perfluorooctanoic acid wastewater, wherein the TOC of raw water is 735mg/L, the raw water is light yellow, the content of chloride ions is 24800mg/L, the total hardness is 187mg/L, the pH is adjusted to 3.5, the hardness is removed by adopting a double-alkali method, the hardness after removal is 31mg/L, and the pH is adjusted back to 6.0; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water;
assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the DC power supply to generate a current of 920A/m2The initial voltage is 5.9V, the retention time is 30min, and the test is started; post oxidation stage, 5% TiO2Colloid, cerium doping 0.5 wt%, iron 0.1% (the amount of iron and cerium is relative to TiO)2Amount of the ultraviolet lamp tube, the ultraviolet lamp tube with the wavelength of 254nm is inserted into the quartz tube after being coated on the quartz tube and roasted for 1 hour at 500 ℃, the ultraviolet lamp tube is arranged according to a group of 5 tubes and three groups of results after being sealed, the retention time is about 30min, and the ultraviolet lamp tube is started during the experiment;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 47mg/L, the effluent is detected by a spectrophotometer, a perfluorooctanoic acid signal exists in an ultraviolet region, and after one week of continuous operation, the average electrochemical energy consumption is 11.2Kwh/m3The voltage is 7.3V;
example 3
Otherwise, the same as example 1
Turning on the intermediate frequency power supply, setting the frequency at 600Hz and the current at 920A/m2Initial voltage of 5.9V, retention time of 30min, start-up during experiment；
As a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 52mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 4
Otherwise, the same as example 1
The intermediate frequency power supply is turned on, the frequency is 1800Hz, and the current is 920A/m2The initial voltage is 5.9V, the retention time is 30min, and the test is started;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 11mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 5
Otherwise, the same as example 1
The intermediate frequency power supply is turned on, the frequency is set to be 1200Hz, and the current is 600A/m2The initial voltage is 5.1V, the retention time is 30min, and the test is started;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 103mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 6
Perfluorooctanoic acid wastewater, wherein the TOC of raw water is 735mg/L, the raw water is light yellow, the content of chloride ions is 24800mg/L, the total hardness is 187mg/L, the pH is adjusted to 3.5, the hardness is removed by adopting a double-alkali method, the hardness after removal is 31mg/L, and the pH is adjusted back to 6.0; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water;
assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the intermediate frequency power supply, setting the frequency at 1200Hz and the current at 920A/m2The initial voltage is 5.9V, the retention time is 30min, and the test is started;
in the post-oxidation process stage, an ultraviolet lamp tube with the wavelength of 254nm is inserted into a quartz tube, no catalyst is loaded on the quartz tube, the quartz tube is sealed and then arranged according to a group of 5 tubes and a group of three results, the residence time is about 30min, and the test is started;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 67mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 7
Perfluorooctanoic acid wastewater, wherein the TOC of raw water is 735mg/L, the raw water is light yellow, the content of chloride ions is 24800mg/L, the total hardness is 187mg/L, the pH is adjusted to 3.5, the hardness is removed by adopting a double-alkali method, the hardness after removal is 31mg/L, and the pH is adjusted back to 6.0; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water;
assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the intermediate frequency power supply, setting the frequency at 1200Hz and the current at 920A/m2The initial voltage is 5.9V, the retention time is 30min, and the test is started;
post oxidation stage, 5% TiO2Colloid, cerium doping 0.5 wt%, iron 0.1% (the amount of iron and cerium is relative to TiO)2Amount of the ultraviolet lamp tube, coating the ultraviolet lamp tube on a quartz tube, roasting at 500 ℃ for 1 hour, inserting the ultraviolet lamp tube with the wavelength of 254nm into the quartz tube, sealing, arranging according to a group of 5 tubes and three groups of results, wherein the retention time is about 30min, and an ultraviolet power supply is not started during an experiment;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 95mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 8
Perfluorooctanoic acid wastewater, wherein the TOC of raw water is 735mg/L, the raw water is light yellow, the content of chloride ions is 24800mg/L, the total hardness is 187mg/L, the pH is adjusted to 3.5, the hardness is removed by adopting a double-alkali method, the hardness after removal is 31mg/L, and the pH is adjusted back to 6.0; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water;
assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the intermediate frequency power supplySetting the frequency of 1200Hz and the current of 600A/m2The initial voltage is 5.1V, the retention time is 30min, and the test is started;
post oxidation stage, 5% TiO2Colloid, cerium doping 0.5 wt%, iron 0.1% (the amount of iron and cerium is relative to TiO)2The amount of the catalyst is that (1), after the catalyst is coated on a quartz tube, the catalyst is roasted for 1 hour at 500 ℃, an ultraviolet lamp tube with the wavelength of 254nm is inserted into the quartz tube, after the catalyst is sealed, the catalyst is arranged according to a group of 5 tubes and three groups of results, the retention time is about 30min, 0.1% hydrogen peroxide is added, and the catalyst is started during the experiment;
as a result, after 8 hours of operation, the effluent is clear and transparent, the TOC is 14mg/L, and no perfluorooctanoic acid signal exists in an ultraviolet region when the TOC is detected by a spectrophotometer;
example 9
Nitrophenol wastewater, wherein the COD of raw water is 3250mg/L, the raw water is deep red, the content of chloride ions is 17500mg/L, the total hardness is 120mg/L, the pH value is adjusted to 6.8, the hardness is removed by adopting a double-alkali method, the hardness after removal is 17mg/L, and the pH value is adjusted back to 6.5; adopting a PP three-compartment electrolytic cell, pumping the wastewater from the bottom to a buffer zone, overflowing to a reaction zone, then overflowing to a post-oxidation zone, and finally discharging water;
assembling electrodes in a reaction zone, wherein the length of the noble metal oxide coating electrode is 50cm, a reticular sleeve is adopted, the outer diameter is 7cm, the inner diameter is 5cm, 5 electrodes are connected in series in one group, and then 3 groups are connected in parallel;
turning on the intermediate frequency power supply, setting the frequency at 1200Hz and the current at 920A/m2The initial voltage is 6.1V, the retention time is 60min, and the test is started;
post oxidation stage, 5% TiO2Colloid, cerium doping 0.5 wt%, iron 0.1% (the amount of iron and cerium is relative to TiO)2Amount of the ultraviolet lamp tube, the ultraviolet lamp tube with the wavelength of 254nm is inserted into the quartz tube after being coated on the quartz tube and roasted for 1 hour at 500 ℃, the ultraviolet lamp tube is arranged according to a group of 5 tubes and three groups of results after being sealed, the retention time is about 30min, and the ultraviolet lamp tube is started during the experiment;
as a result, after 8 hours of operation, the effluent is clear and transparent, the COD is 38mg/L, and the electrochemical average energy consumption is 5.8Kwh/m3(ii) a For each example, the results of the operating parameters are shown in the following table:
| frequency (HZ) | Electric current (A/m)2) | TOC(mg/L) | Remarks for note | |
| Example 1 | 1200 | 920 | 16 | Intermediate frequency power supply |
| Example 2 | 1200 | 920 | 47 | Direct current power supply |
| Example 3 | 600 | 920 | 52 | Intermediate frequency power supply |
| Example 4 | 1800 | 920 | 11 | Intermediate frequency power supply |
| Example 5 | 1200 | 600 | 103 | Intermediate frequency power supply |
| Example 6 | 1200 | 920 | 67 | Intermediate frequency, unsupported catalysts |
| Example 7 | 1200 | 920 | 95 | Intermediate frequency, post oxidation not started |
| Example 8 | 1200 | 600 | 14 | Medium frequency, post oxidation plus 0.1% H2O2 |
| Example 9 | 1200 | 920 | 38 | The data is COD, nitrophenol wastewater |
The comparison between the embodiment 1 and the embodiment 2 shows that the TOC removing effect of the intermediate frequency power supply is better, the average energy consumption is lower, the cell voltage is lower, the energy consumption is reduced, and the service life of the electrode is prolonged; examples 1, 3, 4 examine the effect of frequency on TOC removal, with higher frequency and higher TOC removal and, conversely, lower TOC removal; examples 1 and 5 examine the influence of current density on TOC removal, the current density is high, and the TOC removal rate is high; example 6 compares with example 1 to demonstrate the catalytic importance of the supported catalyst in the post oxidation stage; example 7 compared to example 1 illustrates the importance of strengthening the post oxidation stage; example 8 compares with example 5 to show the importance of the synergistically enhanced post-oxidation process stage, and example 8 compares with example 1 to show that the current density and thus the energy consumption can be reduced, and almost the same effect as example 1 can be achieved by the synergistically enhanced post-oxidation process stage; example 9 illustrates another application scenario of the medium frequency power supply in nitrophenol wastewater.
It should be noted that the embodiment of the present invention adopts an intermediate frequency power supply, but is not limited to the intermediate frequency power supply, and all power supply devices having a function of alternately exchanging positive and negative currents, including but not limited to the intermediate frequency power supply, are within the scope of the present invention.
Claims (10)
1. An apparatus for electrochemical treatment of industrial wastewater by a medium frequency power supply, comprising:
the medium-frequency power supply is used for providing a power supply required by electrochemical treatment of industrial wastewater;
the electrode assembly is used for degrading organic matters in the wastewater through electrochemical reaction;
the electrolytic tank is internally provided with a reaction area for electrochemical reaction of wastewater, one side of the tank body is provided with a wastewater inlet, and the other side of the tank body is provided with a wastewater outlet;
the post oxidation device is arranged behind the electrolytic bath and is used for further oxidizing the wastewater;
the pretreatment device is used for pretreating the pretreated industrial wastewater;
and the circulating pump is arranged between the pretreatment device and the electrolytic bath and is used for conveying the wastewater after pretreatment to the electrolytic bath.
2. One of the above-mentioned compounds according to claim 1The device for electrochemically treating the industrial wastewater by the frequency power supply is characterized in that the current output of the intermediate frequency power supply is a sine curve, the frequency is 400Hz-10KHz, and preferably, the frequency is 500Hz-5 KHz; voltage less than 10V and current 200A/m2-3000A/m2Preferably 800A/m2-2500A/m2。
3. The apparatus as claimed in claim 1, wherein the electrode assembly is graphite, PbO, or PbO2One or a combination of more of ruthenium oxide, iridium oxide, ruthenium iridium oxide, doped ruthenium iridium oxide, Pt, Au, BDD and tin antimony oxide; the shape of the electrode is tubular, reticular or plate-shaped, and the electrodes are combined into one or more groups, preferably, circular reticular.
4. The device for electrochemically treating industrial wastewater by using the intermediate frequency power supply as claimed in claim 3, wherein the cathode and the anode of the electrode can be the same type of electrode or different types of electrodes, and are preferably the cathode and the anode during the working process, and are preferably ruthenium oxide, iridium oxide, ruthenium iridium oxide and doped metal oxide coating electrodes thereof, noble metal electrodes and BDD electrodes.
5. The apparatus of claim 3, wherein the cathode and anode of the electrode are net-shaped and have a sleeve structure.
6. The apparatus of claim 1, wherein the electrolytic cell is corrosion resistant, oxidation resistant, and ultraviolet resistant, and is made of one of PP, PVC, UPVC, FRP, PVDF, glass fiber reinforced plastic, stainless steel, dual phase steel, titanium, and steel-lined plastic.
7. A method for electrochemically treating industrial wastewater by using a medium-frequency power supply according to any one of claims 1 to 6, comprising the steps of:
(1) assembling electrodes in a reaction zone: selecting the length, area and number of groups of electrodes as required, wherein the distance between the cathode plate and the anode plate is 0.5-3cm, adopting a mesh sleeve, the number of the electrodes in series connection is less than 10, and selecting the number of groups in parallel connection as required;
preferably, the distance between the polar plates is 1-1.5cm, the outer tube is 5-7cm, and 5-10 electrodes are connected in series;
(2) pretreating the wastewater by a pretreatment device: removing hard substances of calcium, magnesium and silicon in the wastewater and suspended substances polluting the surface of the electrode so as to reduce the problems of performance and service life attenuation caused by electrode damage caused by voltage rise due to unnecessary factors;
(3) the pretreated wastewater enters from the bottom inlet of the electrolytic cell through a circulating pump, passes through a buffer zone and overflows to a catalytic oxidation reaction zone,
(4) and (3) post-oxidation process stage: the wastewater overflows to a post oxidation device for post oxidation treatment after passing through an electrolytic reaction zone;
(5) turning on the intermediate frequency power supply, setting the frequency of 500Hz-5KHz and the current of 800A/m2-2500A/m2And (3) oxidizing and degrading organic matters by the anode electrode, reacting for 10-120min, and discharging the sewage after the sewage reaches the standard.
8. The method for electrochemically treating industrial wastewater by using the intermediate frequency power supply as claimed in claim 7, wherein the post-oxidation treatment stage is supplemented with hydrogen peroxide, or ultraviolet light, or an ultraviolet light plus catalytic system, preferably, the method comprises activating electrocatalysis by using ultraviolet light to generate active substances, or ultraviolet light is cooperated with an immobilized catalyst.
9. The method for electrochemically treating industrial wastewater by using the intermediate frequency power supply as claimed in claim 8, wherein the ultraviolet light is used to catalytically excite active substances, the ultraviolet light is inserted into the quartz sleeve and then inserted into the wastewater, the ultraviolet light can be arranged in series or in parallel according to the quantity required, the synergistic efficiency of the ultraviolet light is improved, the outer wall of the quartz sleeve is coated by using colloid, and then the quartz sleeve is subjected to high-temperature treatment, wherein the colloid comprises one or more of tungsten, molybdenum, iron and cerium doped with nano titanium dioxide, the doping amount is less than 10%, and preferably, the weight ratio is 0.1-3%.
10. The method for electrochemically treating industrial wastewater by using the medium-frequency power supply as claimed in claim 7, wherein after the wastewater is pretreated, the pH of the wastewater is preferably adjusted to 3-7.
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