CN103304018A - Method and device for enhanced ozone oxidation wastewater treatment of ozone tail gas - Google Patents

Method and device for enhanced ozone oxidation wastewater treatment of ozone tail gas Download PDF

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Publication number
CN103304018A
CN103304018A CN2013102368530A CN201310236853A CN103304018A CN 103304018 A CN103304018 A CN 103304018A CN 2013102368530 A CN2013102368530 A CN 2013102368530A CN 201310236853 A CN201310236853 A CN 201310236853A CN 103304018 A CN103304018 A CN 103304018A
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ozone
tail gas
unit
ozone oxidation
waste water
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CN103304018B (en
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李玉平
李海波
刘晨明
林琳
刘永胜
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Beijing Saike Kanglun Environmental Science & Technology Co Ltd
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Beijing Saike Kanglun Environmental Science & Technology Co Ltd
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Abstract

The invention relates to a method and a device for enhanced ozone oxidation wastewater treatment of ozone tail gas. According to the method, ozone and oxygen in ozone oxidation reaction tail gas are subjected to electrocatalytic reduction to obtain hydrogen peroxide; the hydrogen peroxide catalyzes the ozone to generate hydroxyl radicals; and organic matters in wastewater are mineralized and decomposed. The device comprises a pre-electrolysis unit and an ozone oxidation unit, wherein a tail gas outlet of the ozone oxidation unit is connected to the pre-electrolysis unit. According to the method and the device, oxygen and ozone resources in the tail gas are fully utilized; destroying treatment is not needed; and an ozone oxidation treatment effect is enhanced.

Description

A kind of ozone tail gas is strengthened method and the device of ozone oxidation wastewater treatment
Technical field
The invention belongs to field of waste water treatment, relate in particular to method and device that a kind of ozone tail gas is strengthened the ozone oxidation wastewater treatment.
Background technology
After the biological wastewater treatment, residual organic substances is difficult to biological degradation usually.That these organism have is carcinogenic, teratogenesis and mutagenic " three cause " effect, very harmful, must give deep removal.For the hardly degraded organic substance of these lower concentrations, feasible technology is mainly adsorption and oxidation.Absorption method adopts gac etc. as sorbent material usually, and the loading capacity of gac is limited, and saturated rear regeneration cost is very high, and the saturated discarded carbon of simultaneously hardly degraded organic substance absorption becomes dangerous solid waste and brings secondary pollution.Oxidation technology mainly adopts high-level oxidation technology.In numerous high-level oxidation technologies, the technical finesse costs such as photochemical catalysis, catalytic wet oxidation, electrocatalysis and ultrasonic cavitation are higher, mainly are confined at present the laboratory study stage.The high-level oxidation technology that possesses at present the industrial applications prospect mainly is the Fenton high-level oxidation technology relevant with ozone.Fenton oxidation technology risk is little, and is reliable, but cost is higher, particularly adds iron ion and soda acid adjustment and introduced a large amount of salts in the waste water and be unfavorable for waste water recycling, produces simultaneously the secondary pollution of iron mud.The high-level oxidation technology that ozone is correlated with need not add soda acid usually except the homogeneous phase ozone catalytic, do not produce secondary pollution.Particularly along with the industrialization of Large Efficient rate ozone machine, so that ozone oxidation has more technology competition.Simple ozone oxidation has selectivity, treatment effect to some unsaturated compoundses and aromatic compound is better, but be difficult to the organism permineralization, very poor to organism treatment effects such as some small molecules lipid acid simultaneously, so generally ozone oxidation and additive method are used in conjunction, make it to produce the stronger hydroxyl radical free radical of oxidation capacity, thereby with mineralization of organic material, improving treatment effect, is to utilize the catalyst ozone decomposition to produce hydroxyl radical free radical such as the catalytic ozonation technology.But homogeneous catalyst often brings the heavy metal secondary pollution, and oxide compound heterogeneous catalyst efficient is not high, simultaneously easy inactivation in waste water; Ozone-hydrogen peroxide (O 3/ H 2O 2) technology, utilize hydrogen peroxide catalyzed ozone generation hydroxyl radical free radical, do not introduce catalyst ion, do not have secondary pollution, but the hydrogen peroxide cost that adds is higher, hydrogen peroxide accumulating danger is high.
Particularly based on wastewater treatment, generally adopt source of oxygen, obtain higher ozone concn.Because ozone is difficult to absorb fully and react, still contain certain density ozone in the tail gas after processing, if directly enter atmosphere, can cause air environmental pollution, need to carry out harmless treatment.Main component is oxygen in the tail gas, and other contain a small amount of ozone, water vapor, carbonic acid gas etc., and cost is higher on the one hand to destroy processing up to standard, has wasted on the other hand oxygen and ozone resource.
Summary of the invention
The weak effect and the tail gas that the present invention is directed to existing simple ozone oxidation existence need to destroy the problems such as processing, have proposed method and device that a kind of ozone tail gas is strengthened the ozone oxidation wastewater treatment.
For reaching this purpose, the present invention by the following technical solutions:
One of purpose of the present invention is to provide a kind of ozone tail gas to strengthen the method for ozone oxidation wastewater treatment, and it is hydrogen peroxide that described method makes ozone and oxygen electrical catalyze reduction in the ozone oxidation reaction tail gas; Described hydrogen peroxide catalyzed ozone generation hydroxyl radical free radical decomposes the mineralization of organic material in the waste water.
The method of the invention is utilized ozone and the oxygen resource in the ozone oxidation reaction tail gas, makes it be converted into hydrogen peroxide, strengthens the treatment effect of waste water by ozone oxidation.Electrocatalysis of the present invention and the operation that produces hydroxyl radical free radical all belong to and well known to a person skilled in the art operation.
Particularly, described method makes waste water at first enter the preelectrolysis unit to carry out electrolytic reaction, and the waste water after the electrolytic reaction flows into the ozone oxidation unit; In the ozone oxidation unit, pass into ozone and react, aeration in the ozone tail gas access preelectrolysis unit that the ozone oxidation unit produces.
Waste water after the electrolytic reaction is through pump or from the high-order ozone oxidation unit that certainly flows into.
In the described electrolytic reaction, the control electrolysis voltage is 2～7V, preferred 4V.
Two of purpose of the present invention is to provide a kind of ozone tail gas to strengthen the ozone oxidation wastewater treatment equipment, and described treatment unit comprises preelectrolysis unit and the ozone oxidation unit of connection; The tail gas outlet of described ozone oxidation unit is connected into the preelectrolysis unit.
Described preelectrolysis unit comprises electric catalysis reactor, wherein is provided with anode and negative electrode; Described anode is titanium base ruthenium dioxide or titanium-based titanium dioxide; Described negative electrode is the powder electrode that graphite felt, activated carbon fiber, gac or carbon nanotube and ptfe emulsion adhering and pressing form.The typical but non-limiting example of described negative electrode is: graphite felt, activated carbon fiber, the powder electrode that gac and ptfe emulsion adhering and pressing form, the powder electrode that carbon nanotube and ptfe emulsion adhering and pressing form.
Electric catalysis reactor of the present invention comprises reactor shell, and described anode and negative electrode are positioned at the reactor shell internal space; The reactor shell bottom is provided with aerating apparatus.
Described reactor shell is provided with waste water import, wastewater outlet and tail gas discharging pipe.The concrete setting of described waste water import, wastewater outlet and tail gas discharging pipe can be selected by those skilled in the art, and the present invention there is no particular restriction.Preferably, the waste water import is located at the bottom of reactor shell, wastewater outlet is located at the middle part of reactor shell, and tail gas discharging pipe is located at the top of reactor shell.
The aeration head of described aerating apparatus is pure titanium micro porous aeration head or silica gel micro porous aeration head.Described aeration head is arranged in the below of described negative electrode; Described aerating apparatus air inlet is the ozone tail gas that the ozone oxidation unit produces.
Ozone oxidation of the present invention unit comprises the ozone oxidation reaction device; Described ozone oxidation reaction device bottom is provided with ozone entrance and ozonation aerated device, and top is provided with water-distributing device, and the top is provided with ozone oxidation tail gas discharging pipe and vacuum pressure valves; Described ozone oxidation tail gas discharging pipe is connected into the aerating apparatus of electric catalysis reactor.
The ozone of described ozone oxidation reaction device is oxygen source ozone.
Further, the association reaction principle is described as follows the method for a kind of ozone tail gas reinforcement ozone oxidation of the present invention wastewater treatment:
1, electrocatalysis pre-treatment: the ozone tail gas electrocatalysis is converted into hydrogen peroxide
Waste water is introduced into preelectrolysis unit (electric catalysis reactor), and the ozone tail gas that follow-up ozone oxidation reaction produces passes into this electric catalysis reactor, and the control electrolysis voltage is 2～7V, and ozone and partial oxidation electrical catalyze reduction are hydrogen peroxide, discharge behind the tail gas clean-up.Following principal reaction occurs in the electric catalysis reactor:
O 2+2H 2O+2e→H 2O 2+2OH -
Cathodic reaction: 2O 3+ 6H 2O+6e → 3H 2O 2+ 6OH -
2Cl --2e→Cl 2
Anodic reaction: organism-ne → oxidation products
Cl 2+ organism → oxidation products+2Cl -
Reaction in the solution: H 2O 2+ organism → oxidation products
2, catalytic ozonation
The electric catalysis reactor water outlet enters the ozone oxidation reaction device, and on the one hand, the organism in the waste water is decomposed by ozone oxygen; On the other hand, the hydrogen peroxide catalyzed ozone generation hydroxyl radical free radical in the waste water decomposes oxidation operation.The catalytic ozonation reaction process is mainly as follows:
Ozone oxidation reaction: 2O 3+ organism → oxidation products+2O 2↑+H 2O
2 O 3 + OH - → HO 2 - + O 2
H 2 O 2 + H 2 O → HO 2 - + H 3 O +
The catalytic ozonation reaction: O 3 + HO 2 - → · OH + O 2 - + O 2
OH+ organism → mCO 2+ nH 2O
Compare with the prior art scheme, the present invention has following beneficial effect:
The present invention passes into the tail gas of ozone oxidation reaction in the electric catalysis reactor water inlet, ozone in the tail gas and oxygen in situ electrical catalyze reduction are hydrogen peroxide, and follow-up and ozone reacts, and produce hydroxyl radical free radical, mineralization of organic material is decomposed, thereby strengthened the ozone oxidation effect.By the present invention, not only take full advantage of oxygen and ozone resource in the tail gas, need not destroy processing, strengthened simultaneously the treatment effect of ozone oxidation.
Description of drawings
Fig. 1 is that a kind of ozone tail gas of the present invention is strengthened the ozone oxidation wastewater treatment equipment.
Among the figure: the 1-reactor shell; The 2-anode; The 3-negative electrode; The 4-aerating apparatus; The 5-tail gas discharging pipe; The ozonation aerated device of 6-; The 7-water-distributing device; 8-ozone oxidation tail gas discharging pipe; The 9-vacuum pressure valves; 10-waste water; Waste water after the 11-electrolytic reaction; The 12-ozone tail gas; 13-ozone; The unit water outlet of 14-ozone oxidation.
Below the present invention is described in more detail.But following example only is simple and easy example of the present invention, does not represent or limit the scope of the present invention, and protection scope of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
As shown in Figure 1, a kind of ozone tail gas is strengthened the ozone oxidation wastewater treatment equipment, and described treatment unit comprises preelectrolysis unit and the ozone oxidation unit of connection; The tail gas outlet of described ozone oxidation unit is connected into the preelectrolysis unit.
Described preelectrolysis unit comprises electric catalysis reactor, and described electric catalysis reactor comprises reactor shell 1, and its internal space is provided with anode 2 and negative electrode 3; Described anode 2 is titanium base ruthenium dioxide or titanium-based titanium dioxide; Described negative electrode 3 is the powder electrode that graphite felt, activated carbon fiber, gac or carbon nanotube and ptfe emulsion adhering and pressing form.
Reactor shell 1 bottom is provided with aerating apparatus 4; Described reactor shell 1 is provided with waste water import, wastewater outlet and tail gas discharging pipe 5.The aeration head of described aerating apparatus 4 is pure titanium micro porous aeration head or silica gel micro porous aeration head; Described aeration head is arranged in the below of described negative electrode 3; Described aerating apparatus 4 air inlets are the ozone tail gas 12 that the ozone oxidation unit produces.
Described ozone oxidation unit comprises the ozone oxidation reaction device; Described ozone oxidation reaction device bottom is provided with ozone entrance and ozonation aerated device 6, and top is provided with water-distributing device 7, and the top is provided with ozone oxidation tail gas discharging pipe 8 and vacuum pressure valves 9; Described ozone oxidation tail gas discharging pipe 8 is connected into the aerating apparatus 4 of electric catalysis reactor.
The ozone of described ozone oxidation reaction device is oxygen source ozone.
Embodiment 1
The advanced treatment object is the coking chemical waste water after carrying out a biological disposal upon, and COD is about 150mg/L.
Waste water 10 at first enters the preelectrolysis unit and carries out electrolytic reaction, the control electrolysis voltage is 2V, and the ozone tail gas 12 that follow-up ozone reaction produces passes into this electric catalysis reactor simultaneously, and anode 2 adopts titanium base ruthenium dioxide plate, negative electrode 3 is graphite felt, and aerating apparatus 4 is pure titanium aeration head.Waste water 11(after the electrolytic reaction contains hydrogen peroxide) squeeze into the ozone oxidation unit through pump, in the ozone oxidation reaction device, pass into ozone 13 and react, the ozone that ozone 13 produces for source of oxygen, the ozone add-on is 100mg/L.Aerating apparatus 4 in the ozone tail gas 12 access preelectrolysis unit that the ozone oxidation unit produces.Obtain at last ozone oxidation unit water outlet 14, COD is 20～50mg/L, and ozone is lower than 0.5ppm in the tail gas of preelectrolysis unit discharging.
Embodiment 2
The advanced treatment object is the lincomycin wastewater after carrying out a biological disposal upon, and COD is about 300mg/L.
Waste water 10 at first enters the preelectrolysis unit and carries out electrolytic reaction, the control electrolysis voltage is 7V, the ozone tail gas 12 that follow-up ozone reaction produces passes into this electric catalysis reactor simultaneously, anode 2 adopts the titanium-based titanium dioxide plate, negative electrode 3 is the powder electrode that gac and ptfe emulsion adhering and pressing form, and aerating apparatus 4 is pure titanium aeration head.Waste water 11(after the electrolytic reaction contains hydrogen peroxide) squeeze into the ozone oxidation unit through pump, in the ozone oxidation reaction device, pass into ozone 13 and react, the ozone that ozone 13 produces for source of oxygen, the ozone add-on is 200mg/L.Aerating apparatus 4 in the ozone tail gas 12 access preelectrolysis unit that the ozone oxidation unit produces.Obtain at last ozone oxidation unit water outlet 14, COD is 100～150mg/L, and ozone is lower than 0.5ppm in the tail gas of preelectrolysis unit discharging.
Embodiment 3
The advanced treatment object is the dyeing waste water after carrying out a biological disposal upon, and COD is about 250mg/L.
Waste water 10 at first enters the preelectrolysis unit and carries out electrolytic reaction, the control electrolysis voltage is 4V, and the ozone tail gas 12 that follow-up ozone reaction produces passes into this electric catalysis reactor simultaneously, and anode 2 adopts the titanium-based titanium dioxide plate, negative electrode 3 is activated carbon fiber, and aerating apparatus 4 is the silica gel aeration head.Waste water 11(after the electrolytic reaction contains hydrogen peroxide) squeeze into the ozone oxidation unit through pump, in the ozone oxidation reaction device, pass into ozone 13 and react, the ozone that ozone 13 produces for source of oxygen, the ozone add-on is 150mg/L.Aerating apparatus 4 in the ozone tail gas 12 access preelectrolysis unit that the ozone oxidation unit produces.Obtain at last ozone oxidation unit water outlet 14, COD is 80～100mg/L, and ozone is lower than 0.5ppm in the tail gas of preelectrolysis unit discharging.
Embodiment 4
The advanced treatment object is the paper waste after carrying out a biological disposal upon, and COD is about 300mg/L.
Waste water 10 at first enters the preelectrolysis unit and carries out electrolytic reaction, the control electrolysis voltage is 3V, the ozone tail gas 12 that follow-up ozone reaction produces passes into this electric catalysis reactor simultaneously, anode 2 adopts the titanium-based titanium dioxide plate, negative electrode 3 is the powder electrode that carbon nanotube and ptfe emulsion adhering and pressing form, and aerating apparatus 4 is the silica gel aeration head.Waste water 11(after the electrolytic reaction contains hydrogen peroxide) squeeze into the ozone oxidation unit through pump, in the ozone oxidation unit, pass into ozone 13 and react, the ozone that ozone 13 produces for source of oxygen, the ozone add-on is 300mg/L.Aerating apparatus 4 in the ozone tail gas 12 access preelectrolysis unit that the ozone oxidation unit produces.Obtain at last ozone oxidation unit water outlet 14, COD is 100～150mg/L, and ozone is lower than 0.5ppm in the tail gas of preelectrolysis unit discharging.
Applicant's statement, the present invention illustrates detailed structure feature of the present invention and treatment process by above-described embodiment, but the present invention is not limited to above-mentioned detailed structure feature and treatment process, does not mean that namely the present invention must rely on above-mentioned detailed structure feature and treatment process could be implemented.The person of ordinary skill in the field should understand, any improvement in the present invention to the increase of the equivalence replacement of the selected parts of the present invention and accessory, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.

Claims (10)

1. the method for ozone tail gas reinforcement ozone oxidation wastewater treatment is characterized in that, it is hydrogen peroxide that described method makes ozone and oxygen electrical catalyze reduction in the ozone oxidation reaction tail gas; Described hydrogen peroxide catalyzed ozone generation hydroxyl radical free radical decomposes the mineralization of organic material in the waste water.
2. the method for claim 1 is characterized in that, described method makes waste water (10) at first enter the preelectrolysis unit to carry out electrolytic reaction, and the waste water after the electrolytic reaction (11) flows into the ozone oxidation unit; In the ozone oxidation unit, pass into ozone and react, aeration in ozone tail gas (12) the access preelectrolysis unit that the ozone oxidation unit produces.
3. method as claimed in claim 2 is characterized in that, the waste water after the electrolytic reaction (11) is through pump or from the high-order ozone oxidation unit that certainly flows into.
4. method as claimed in claim 2 or claim 3 is characterized in that, in the described electrolytic reaction, the control electrolysis voltage is 2～7V, preferred 4V.
5. a realization is characterized in that such as the treatment unit of method as described in one of claim 1-4, and described treatment unit comprises preelectrolysis unit and the ozone oxidation unit of connection; The tail gas outlet of described ozone oxidation unit is connected into the preelectrolysis unit.
6. treatment unit as claimed in claim 5 is characterized in that, described preelectrolysis unit comprises electric catalysis reactor, wherein is provided with anode (2) and negative electrode (3); Described anode (2) is titanium base ruthenium dioxide or titanium-based titanium dioxide; Described negative electrode (3) is the powder electrode that graphite felt, activated carbon fiber, gac or carbon nanotube and ptfe emulsion adhering and pressing form.
7. treatment unit as claimed in claim 6 is characterized in that, described electric catalysis reactor comprises reactor shell (1), and described anode (2) and negative electrode (3) are positioned at reactor shell (1) internal space; Reactor shell (1) bottom is provided with aerating apparatus (4);
Preferably, described reactor shell (1) is provided with waste water import, wastewater outlet and tail gas discharging pipe (5).
8. treatment unit as claimed in claim 7 is characterized in that, the aeration head of described aerating apparatus (4) is pure titanium micro porous aeration head or silica gel micro porous aeration head;
Preferably, described aeration head is arranged in the below of described negative electrode (3);
Preferably, described aerating apparatus (4) air inlet is the ozone tail gas (12) that the ozone oxidation unit produces.
9. such as the described treatment unit of one of claim 5-8, it is characterized in that, described ozone oxidation unit comprises the ozone oxidation reaction device; Described ozone oxidation reaction device bottom is provided with ozone entrance and ozonation aerated device (6), and top is provided with water-distributing device (7), and the top is provided with ozone oxidation tail gas discharging pipe (8) and vacuum pressure valves (9); Described ozone oxidation tail gas discharging pipe (8) is connected into the aerating apparatus (4) of electric catalysis reactor.
10. treatment unit as claimed in claim 9 is characterized in that, the ozone of described ozone oxidation reaction device is oxygen source ozone.
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CN104710053A (en) * 2015-03-03 2015-06-17 中北大学 Method and device for strengthened ozone treatment of nitrobenzene waste water in high gravity filed
CN105253960A (en) * 2015-11-23 2016-01-20 雅本化学股份有限公司 Wastewater treatment device and method for treating wastewater by adopting wastewater treatment device
CN106810017A (en) * 2015-12-01 2017-06-09 中国科学院过程工程研究所 A kind of difficult degradation industrial organic waste water advanced treatment apparatus and technique
CN106830457A (en) * 2017-03-23 2017-06-13 博瑞德（南京）净化技术有限公司 Electrode couples ozone oxidation integral reactor
CN106830417A (en) * 2017-01-12 2017-06-13 新宇药业股份有限公司 The processing method of lincomycin in a kind of efficient degradation waste water
CN106882866A (en) * 2017-02-24 2017-06-23 河北科技大学 The method that hydrogen peroxide synergy ozone heterogeneous catalytic oxidation processes waste water
CN107200394A (en) * 2017-07-18 2017-09-26 中国科学院生态环境研究中心 A kind of electro-catalysis ozone high grade oxidation membrane reactor wastewater treatment equipment and method
CN108217862A (en) * 2018-03-08 2018-06-29 中国石油大学(北京) A kind of bipolar electrode electric flocculation-electro-catalysis ozone equipment and process for treating industrial waste water
CN110143706A (en) * 2019-06-18 2019-08-20 中南大学 A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone
CN111646625A (en) * 2020-06-19 2020-09-11 见嘉环境科技（苏州）有限公司 Water treatment device adopting multistage electrocatalysis evaporation and application method
CN112897768A (en) * 2021-01-25 2021-06-04 哈尔滨工业大学（威海） Electrochemical/ozone catalytic composite device and organic pollution wastewater treatment method
CN114716001A (en) * 2022-05-17 2022-07-08 苏州清缘环保科技有限公司 Device and method for treating refractory organic matters by in-situ electricity generated hydrogen peroxide and ozone
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CN103990366A (en) * 2014-05-20 2014-08-20 江苏大学 Method and system for removing mercury through free radicals generated based on ozone/hydrogen peroxide
CN104710053A (en) * 2015-03-03 2015-06-17 中北大学 Method and device for strengthened ozone treatment of nitrobenzene waste water in high gravity filed
CN105253960A (en) * 2015-11-23 2016-01-20 雅本化学股份有限公司 Wastewater treatment device and method for treating wastewater by adopting wastewater treatment device
CN106810017A (en) * 2015-12-01 2017-06-09 中国科学院过程工程研究所 A kind of difficult degradation industrial organic waste water advanced treatment apparatus and technique
CN106810017B (en) * 2015-12-01 2020-06-16 中国科学院过程工程研究所 Advanced treatment device and process for refractory industrial organic wastewater
CN106830417A (en) * 2017-01-12 2017-06-13 新宇药业股份有限公司 The processing method of lincomycin in a kind of efficient degradation waste water
CN106882866A (en) * 2017-02-24 2017-06-23 河北科技大学 The method that hydrogen peroxide synergy ozone heterogeneous catalytic oxidation processes waste water
CN106830457A (en) * 2017-03-23 2017-06-13 博瑞德（南京）净化技术有限公司 Electrode couples ozone oxidation integral reactor
CN106830457B (en) * 2017-03-23 2023-10-13 博瑞德环境集团股份有限公司 Electrode coupling ozone oxidation integrated reactor
CN107200394B (en) * 2017-07-18 2021-01-29 中国科学院生态环境研究中心 Electro-catalytic ozone advanced oxidation membrane reactor wastewater treatment device and method
CN107200394A (en) * 2017-07-18 2017-09-26 中国科学院生态环境研究中心 A kind of electro-catalysis ozone high grade oxidation membrane reactor wastewater treatment equipment and method
CN108217862A (en) * 2018-03-08 2018-06-29 中国石油大学(北京) A kind of bipolar electrode electric flocculation-electro-catalysis ozone equipment and process for treating industrial waste water
CN108217862B (en) * 2018-03-08 2020-12-08 中国石油大学(北京) Double-electrode electric flocculation-electrocatalysis ozone device and industrial wastewater treatment method
CN110143706A (en) * 2019-06-18 2019-08-20 中南大学 A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone
CN111646625A (en) * 2020-06-19 2020-09-11 见嘉环境科技（苏州）有限公司 Water treatment device adopting multistage electrocatalysis evaporation and application method
CN112897768A (en) * 2021-01-25 2021-06-04 哈尔滨工业大学（威海） Electrochemical/ozone catalytic composite device and organic pollution wastewater treatment method
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