CN105329990A - Device and method for performing ultrasonic-enhanced electrocatalytic oxidation treatment on reverse osmosis concentrated water - Google Patents
Device and method for performing ultrasonic-enhanced electrocatalytic oxidation treatment on reverse osmosis concentrated water Download PDFInfo
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- CN105329990A CN105329990A CN201510711239.4A CN201510711239A CN105329990A CN 105329990 A CN105329990 A CN 105329990A CN 201510711239 A CN201510711239 A CN 201510711239A CN 105329990 A CN105329990 A CN 105329990A
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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
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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Abstract
The invention discloses a device and method for performing ultrasonic-enhanced electrocatalytic oxidation treatment on reverse osmosis concentrated water. The device comprises an enhanced electrocatalytic oxidation system (8), a settling zone (5), a water inlet (3), an annular flow guiding plate (4), a water outlet (2), a flow guiding zone (6), a mud discharge port (7) and a power supply control system (13). The method comprises the steps that the reverse osmosis concentrated water enters the device from the water inlet (3) and enters the enhanced electrocatalytic oxidation system (8) from the bottom of the flow guiding zone (6); the power supply control system (13) supplies a direct-current power supply to the enhanced electrocatalytic oxidation system (8); part of yielding water of the enhanced electrocatalytic oxidation system (8) is drained from the water outlet (2), the other part of the yielding water is circulated to the bottom of a reactor to be mixed with feeding water, and the yielding water and the feeding water jointly enter the enhanced electrocatalytic oxidation system (8) from the flow guiding zone (6) again; scale slag is generated in the electrolytic process, mud-water separation is achieved through the settling zone (5), and the scale slag is discharged from the mud discharge port (7). According to the method and device, the electrocatalytic oxidation treatment capacity is enhanced, and the operation efficiency and stability of the system are improved.
Description
Technical field
The invention belongs to environmental engineering field of waste water treatment, relate to a kind of wastewater processing technology, particularly a kind of device and method of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water.
Background technology
In recent years, waste water is produced in the Industrial processes such as petrochemical complex, metallurgy and Circulating water effluent water problems is more and more outstanding.Reverse osmosis membrane technology is as the process of a kind of waste water depths and technology of middle water recycle, become the important technology of trade effluent and recirculated water reuse gradually, but because reverse osmosis process generally produces the dense water of film of about 30%, the general saltiness of such waste water is higher, especially after the multistage-combination art breading of front end, a large amount of difficult degradation class material aggregation is in the dense water of film, and as benzene class, biphenyl class material, lopps material etc., traditional biological and materializing strategy are difficult to meet processing requirements.Therefore, the dense water treatment problems of film becomes the technical barrier that reverse osmosis technology is applied.Electro-catalytic oxidation technology is as a kind of advanced oxidation treatment technology, it is by producing Strong oxdiative group at electrode surface, as hydroxyl radical free radical, pollutent thorough mineralising in polar board surface or aqueous phase is made to be carbonic acid gas and water, realize effectively removing fast of pollutent, therefore, electro-catalytic oxidation technology is used for the dense water treatment of reverse osmosis membrane and there is very large technical superiority.But also there are some technical problems in common electro-catalytic oxidation technology in the dense water of process reverse osmosis membrane, thus limit the application of its further genralrlization, be mainly manifested in the following aspects: 1) pollutant oxidation is removed not thorough, especially, for some macromole hardly degraded organic substances, after open loop, chain rupture, be difficult to its mineralising thoroughly, and along with the reduction of Pollutant levels, electrolytic efficiency significantly declines, and energy consumption increases, and processing cost increases greatly; 2) in catalytic and oxidative electrolysis technology process, organic pollutant is finally carbonic acid gas and water by mineralising, and generating portion gas, because produced bubble is minimum, homogeneity air-water mixture is formed with water, and concentrate near pole plate, reduce catalytic and oxidative electrolysis technology unit anode and cathode electrical efficiency, affect catalytic degradation efficiency; 3) easily produce " concentration polarization " phenomenon at polar board surface, along with concentration polarization strengthens, electrolytic efficiency declines, and pollutant removal is deteriorated; 4), after long-play, the especially higher sewage of saltiness, pole plate resistance to crocking reduces, and amount of scale buildup increases, influential system operation stability and effluent quality.Therefore, urgently solving the problems of the technologies described above, is the key realizing reverse osmosis concentrated water advanced treatment.
Summary of the invention
In order to overcome above-mentioned technical deficiency, the object of this invention is to provide a kind of device and method of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water, adopt ultrasonic synergistic catalytic oxidation co-treatment reverse osmosis concentrated water, running efficiency of system and stability can be significantly improved, can running cost be reduced again.
The present invention is a kind of device of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water, this device comprises cylindrical case, the top of cylindrical case is provided with water outlet, bottom is provided with water-in and ring diversion plate, described water-in is positioned at the top of ring diversion plate, settling region is formed inside ring diversion plate, outside forms guiding region, the below of settling region is provided with mud discharging mouth, strengthening catalytic oxidation system is provided with around central shaft in cylindrical case, described strengthening catalytic oxidation system is alternately arranged by several catalytic and oxidative electrolysis technology unit and ultrasonic wave generating unit and forms, number >=4 of catalytic and oxidative electrolysis technology unit and ultrasonic wave generating unit, concrete quantity is according to the dense water water yield of reverse osmosis membrane, water quality and determining,
Described catalytic and oxidative electrolysis technology unit is made up of center cylindricality anode and telescopic negative electrode, and catalytic and oxidative electrolysis technology unit and ultrasonic wave generating unit control electric current, voltage and ultrasonic power by power control system and export;
Wherein said settling region is separated by ring diversion plate and catalytic and oxidative electrolysis technology unit, and settling region bucket and level angle are not less than 40 DEG C.
In device of the present invention, described center cylindricality anode be preferably high effective and modified electrode, electrode take metal titanium as base material, by nickel, manganese, platinum, palladium wherein one or more materials composition coating solution, by dipping, sinter process obtain; Described telescopic negative electrode is preferably high purity metal titanium base material.
Present invention also offers a kind of method of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water, the method comprises: adopt combined treatment device process reverse osmosis concentrated water of the present invention, reverse osmosis concentrated water is entered by water-in, strengthening catalytic oxidation system is entered by bottom by flow deflector, by power control system for strengthening catalytic oxidation system provides direct supply, a strengthening catalytic oxidation system water outlet part is discharged by water outlet, a part is circulated to reactor bottom and mixes jointly again enter intensified electrolysis catalytic oxidation system by guiding region with water inlet, produce dirty slag in electrolytic process and realize mud-water separation by settling region, dirt slag is discharged by mud discharging mouth, wherein reverse osmosis concentrated water reaction times in device controls at 20min ~ 40min.
Method of the present invention, wherein said catalytic and oxidative electrolysis technology unit is under power control system outward current condition, reverse osmosis concentrated water is promoted to top from catalytic oxidation unit bottom, realize reverse osmosis concentrated water in device internal recycling, circulation ratio is with power control system outward current size variation.
Method of the present invention, wherein said catalytic and oxidative electrolysis technology unit loads power supply for direct supply, and preferred electric current is at 0 ~ 300A, specifically adjustable according to reverse osmosis membrane dense water water quality; The described preferred output rating of ultrasonic wave generating unit is 100w ~ 1000w, and output frequency is 20KHz ~ 40KHz, specifically adjustable according to reverse osmosis concentrated water water quality.
Compared with prior art, the present invention has following technical characterstic:
1, the present invention adopts unique catalytic oxidation system design, catalytic and oxidative electrolysis technology unit is under external dc power supply condition, dense water is promoted to top by electrolytic catalysis unit bottom, thus realize dense water and circulate in catalytic oxidation internal system, and according to impressed current size, control dense water in system internal recycle multiplying power, make pollutent obtain repeatedly fully exhaustive oxidation, strengthening catalytic oxidation systemic contamination thing removal efficiency.
2, the present invention is by installing ultrasonic wave generating unit and catalytic and oxidative electrolysis technology units alternately, under ul-trasonic irradiation, macromole hardly degraded organic substance molecular structure will change, and impel its chemical bond mechanical vibration and breakdown rate, contribute to further deep oxidation and remove.In addition, under ul-trasonic irradiation, by pole plate katalysis, impel catalytic oxidation system to produce more poly-hydroxy free radical, significantly improve catalytic oxidation system contaminant removal capacity and speed.
3, the carbonic acid gas produced in electrolytic process and portion gas are attached to polar board surface with micro-bubble form, by ultrasonic cavitation effect, high temperature, hyperbaric environment can be formed around micro-bubble, promote hardly degraded organic substance chemical bond rupture and degradation rate, thus collaborative catalytic and oxidative electrolysis technology system improves this device oxidation efficiency further, saves operation energy consumption.
4, under ul-trasonic irradiation, catalytic oxidation system Inner electrolysis matter uniformity coefficient can be significantly improved, make polar board surface pollutent rapid diffusion, slow down polar board surface " concentration polarization " phenomenon, improve electrolytic efficiency, and by ultrasonic cleaning effect, polar board surface pollutent can be removed further, the pole plate dirty slag that comes off realizes mud-water separation in settling region, avoids again being circulated in catalytic and oxidative electrolysis technology unit, thus improves effluent quality further.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of a kind of intensified by ultrasonic wave catalytic oxidation of the present invention process reverse osmosis concentrated water.
Fig. 2 is the schematic top plan view of the device of Fig. 1.
Wherein, 1, cylindrical case; 2, water outlet; 3, water-in; 4, ring diversion plate; 5, settling region; 6, guiding region; 7, mud discharging mouth; 8, catalytic oxidation system is strengthened; 9, catalytic and oxidative electrolysis technology unit; 10, ultrasonic wave generating unit; 11, center cylindricality anode; 12, telescopic negative electrode; 13 power control systems.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.
Fig. 1-2 provides the device of a kind of intensified by ultrasonic wave catalytic oxidation of the present invention process reverse osmosis concentrated water, and this device comprises cylindrical case 1, strengthening catalytic oxidation system 8, settling region 5, water-in 3, ring diversion plate 4, water outlet 2, guiding region 6, mud discharging mouth 7 and power control system 13; Reverse osmosis concentrated water is entered by water-in 3, strengthening catalytic oxidation system 8 is entered by bottom by guiding region 6, by power control system 13 for strengthening catalytic oxidation system 8 provides direct supply, a strengthening catalytic oxidation system 8 water outlet part is discharged by water outlet 2, a part is circulated to reactor bottom and mix jointly again to be entered by guiding region 6 with water inlet and strengthen catalytic oxidation system 8, produce dirty slag in electrolytic process and realize mud-water separation by settling region 5, dirty slag is discharged by mud discharging mouth 7.
As shown in the figure, strengthening catalytic oxidation system 8 is alternately arranged by several catalytic and oxidative electrolysis technology unit 9 and ultrasonic wave generating unit 10 and forms (in figure, embodiment is 4), reverse osmosis concentrated water reaction times in device controls at 20min ~ 40min, and the concrete quantity of catalytic and oxidative electrolysis technology unit 9 and ultrasonic wave generating unit 10 and reaction times are according to the reverse osmosis concentrated water water yield, water quality and determining.
Described catalytic and oxidative electrolysis technology unit 9 is under power control system 13 outward current condition, reverse osmosis concentrated water is promoted to top bottom catalytic and oxidative electrolysis technology unit 9, realize reverse osmosis concentrated water in device internal recycling, circulation ratio is with power control system 13 outward current size variation.
Described catalytic and oxidative electrolysis technology unit 9 is made up of center cylindricality anode 11 and telescopic negative electrode 12, and catalytic and oxidative electrolysis technology unit 9 and ultrasonic wave generating unit 10 control electric current, voltage and ultrasonic power by power control system 13 and export.
Described settling region 5 is separated by ring diversion plate 4 and catalytic and oxidative electrolysis technology unit 9, and settling region bucket and level angle are not less than 40 DEG C.
Described center cylindricality anode 11 is high effective and modified electrode, and electrode take metal titanium as base material, by nickel, manganese, platinum, palladium wherein one or more materials composition coating solution, by dipping, sinter process obtain; Described telescopic negative electrode 12 is high purity metal titanium base material.
Described catalytic and oxidative electrolysis technology unit 9 loads power supply for direct supply, and electric current is at 0 ~ 300A, specifically adjustable according to reverse osmosis membrane dense water water quality; Described ultrasonic wave generating unit 10 output rating is 100w ~ 1000w, and output frequency is 20KHz ~ 40KHz, specifically adjustable according to reverse osmosis concentrated water water quality.
Embodiment one:
Zhanjiang, Guangdong Province petro-chemical corporation adopts reverse osmosis system advanced treating secondary bio-chemical effluent to be used for Treated sewage reusing, and feed water by reverse osmosis derives from front end secondary biochemical treatment, and the dense water of reverse osmosis membrane is about 120m
3/ d, in the dense water of film, saltiness is high, and containing a large amount of hardly degraded organic substance material, as phenyl ring and chelate structure pollutent, adopts common biochemical treatment to be difficult to satisfied local emission standard.
The device and method of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water of the present invention is adopted to carry out 6m to the dense water of the said firm's reverse osmosis membrane
3the pilot plant test of/d, reverse osmosis concentrated water COD between 178 ~ 238mg/L, average out to 198mg/L, reverse osmosis concentrated water is 30min in the device residence time, direct supply outward current is 200A, ultrasonic power output is 300W, and frequency is 25KHz, after apparatus of the present invention process, water outlet COD is between 36 ~ 47mg/L, average out to 41mg/L, COD average removal rate reaches 79%, and water outlet meets manufacturer's emission standard.
Embodiment two:
Ningbo City, Zhejiang Province petro-chemical corporation adopts filtration-reverse osmosis system depth process secondary biochemical effluent, and reverse osmosis produced water is used for plant area's circulating cooling make-up water, and the dense water of reverse osmosis membrane is about 960m
3/ d, contains a large amount of difficult degradation lopps material in the dense water of film and saltiness is higher, and adopt traditional chemical oxidation and biologic treating technique to be difficult to meet processing requirements, factory building is intended carrying out upgrading to the dense water technology of reverse osmosis membrane.
The device and method of intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water of the present invention is adopted to carry out 12m to the dense water of the said firm's reverse osmosis membrane
3the pilot plant test of/d, reverse osmosis concentrated water COD between 158 ~ 278mg/L, average out to 218mg/L, reverse osmosis concentrated water is 40min in the device residence time, direct supply outward current is 300A, ultrasonic power output is 600W, and frequency is 35KHz, after apparatus of the present invention process, water outlet COD is between 58 ~ 72mg/L, average out to 62mg/L, COD average removal rate reaches 72%, and effluent quality meets manufacturer's specified requirement.
Claims (4)
1. the device of an intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water, it is characterized in that, comprise cylindrical case (1), cylindrical case (1) top is provided with water outlet (2), bottom is disposed with water-in (3) and ring diversion plate (4), described water-in (3) is positioned at the top of ring diversion plate (4), ring diversion plate (4) inner side forms settling region (5), outside forms guiding region (6), the below of settling region (5) is provided with mud discharging mouth (7), strengthening catalytic oxidation system (8) is provided with around cylindrical case (1) interior central shaft, described strengthening catalytic oxidation system (8) is alternately arranged by several catalytic and oxidative electrolysis technology unit (9) and ultrasonic wave generating unit (10) and forms, catalytic and oxidative electrolysis technology unit (9) and ultrasonic wave generating unit (10) number >=4, concrete quantity is according to the dense water water yield of reverse osmosis membrane, water quality and determining,
Described catalytic and oxidative electrolysis technology unit (9) is made up of center cylindricality anode (11) and telescopic negative electrode (12), and catalytic and oxidative electrolysis technology unit (9) and ultrasonic wave generating unit (10) control electric current, voltage and ultrasonic power by power control system (13) and export;
Wherein said settling region (5) is separated by ring diversion plate (4) and catalytic and oxidative electrolysis technology unit (9), and settling region (5) bucket and level angle are not less than 40 DEG C.
2. device according to claim 1, it is characterized in that: described center cylindricality anode (11) is high effective and modified electrode, electrode take metal titanium as base material, by nickel, manganese, platinum, palladium wherein one or more materials composition coating solution, by dipping, sinter process obtain; Described telescopic negative electrode (12) is high purity metal titanium base material.
3. the method for an intensified by ultrasonic wave catalytic oxidation process reverse osmosis concentrated water, it is characterized in that, comprise: adopt device process reverse osmosis concentrated water according to claim 1, reverse osmosis concentrated water is entered by water-in (3), strengthening catalytic oxidation system (8) is entered by bottom by guiding region (6), by power control system (13) for strengthening catalytic oxidation system (8) provides direct supply, strengthening catalytic oxidation system (8) water outlet part is discharged by water outlet (2), a part is circulated to reactor bottom and mix jointly again to be entered by guiding region (6) with water inlet and strengthen catalytic oxidation system (8), produce dirty slag in electrolytic process and realize mud-water separation by settling region (5), dirt slag is discharged by mud discharging mouth (7),
Wherein reverse osmosis concentrated water reaction times in device controls at 20min ~ 40min.
4. method according to claim 3, is characterized in that: described catalytic and oxidative electrolysis technology unit (9) loads power supply for direct supply, and electric current is at 0 ~ 300A, specifically adjustable according to reverse osmosis concentrated water water quality; Described ultrasonic wave generating unit (10) output rating is 100w ~ 1000w, and output frequency is 20KHz ~ 40KHz, specifically adjustable according to reverse osmosis concentrated water water quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105967313A (en) * | 2016-06-21 | 2016-09-28 | 中国海洋石油总公司 | Internal recycle photoelectron-catalytic oxidation combined treatment device |
| CN109231606A (en) * | 2018-11-24 | 2019-01-18 | 江苏卓博环保科技有限公司 | Cotton Pulp Wastewater advanced treatment and reclamation devices and methods therefor |
| CN112679008A (en) * | 2020-12-14 | 2021-04-20 | 江苏卓博环保科技有限公司 | Reverse osmosis concentrated water multi-stage combined technology treatment device and treatment method |
| EP4263439A4 (en) * | 2020-12-17 | 2024-05-01 | Axine Water Tech Inc | Method and system for wastewater treatment by membrane filtration and electrochemical oxidation |
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| EP4263439A4 (en) * | 2020-12-17 | 2024-05-01 | Axine Water Tech Inc | Method and system for wastewater treatment by membrane filtration and electrochemical oxidation |
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