CN105329990B - A kind of intensified by ultrasonic wave electrocatalytic oxidation processes the device and method of reverse osmosis concentrated water - Google Patents
A kind of intensified by ultrasonic wave electrocatalytic oxidation processes the device and method of reverse osmosis concentrated water Download PDFInfo
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- CN105329990B CN105329990B CN201510711239.4A CN201510711239A CN105329990B CN 105329990 B CN105329990 B CN 105329990B CN 201510711239 A CN201510711239 A CN 201510711239A CN 105329990 B CN105329990 B CN 105329990B
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- reverse osmosis
- water
- electrocatalytic oxidation
- concentrated water
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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
Abstract
The invention discloses the device and method that a kind of intensified by ultrasonic wave electrocatalytic oxidation processes reverse osmosis concentrated water, the device includes reinforcing electrocatalytic oxidation system (8), settling zone (5), water inlet (3), ring diversion plate (4), delivery port (2), guiding region (6), mud discharging mouth (7) and power control system (13).The method includes：Reverse osmosis concentrated water is entered by water inlet (3), reinforcing electrocatalytic oxidation system (8) is entered by bottom by guiding region (6), by power control system (13) for reinforcing electrocatalytic oxidation system (8) provides dc source, reinforcing electrocatalytic oxidation system (8) water outlet part is discharged by delivery port (2), a part is recycled to reactor bottom and mix with water inlet and common is again introduced into strengthening electrocatalytic oxidation system (8) by guiding region (6), dirty slag is produced to realize mud-water separation by settling zone (5) in electrolytic process, dirty slag is discharged by mud discharging mouth (7).Invention enhances electrocatalytic oxidation disposal ability, running efficiency of system and stability are improve.
Description
Technical field
The invention belongs to environmental project field of waste water treatment, it is related to a kind of wastewater processing technology, particularly a kind of ultrasonic wave
Reinforcing electrocatalytic oxidation processes the device and method of reverse osmosis concentrated water.
Background technology
In recent years, waste water and Circulating water effluent water problems are produced increasingly in the industrial processes such as petrochemical industry, metallurgy
It is prominent.Reverse osmosis membrane technology is processed and technology of middle water recycle as a kind of waste water depths, has been increasingly becoming industrial wastewater and has been followed
The important technology of ring Water circulation, but 30% or so film concentrated water is typically produced due to reverse osmosis process, the general saliferous of such waste water
Amount is higher, especially by after the multistage-combination PROCESS FOR TREATMENT of front end, a large amount of difficult degradation class material aggregations in film concentrated water, such as benzene
Class, connection benezene material, ring class material etc., traditional biological and materializing strategy are difficult to meet processing requirement.Therefore, film concentrated water treatment is asked
Technical barrier of the topic as reverse osmosis technology popularization and application.Electro-catalytic oxidation technology as a kind of advanced oxidation treatment technology, it
The Strong oxdiative group, such as hydroxyl radical free radical is produced to make pollutant thorough mineralising in polar board surface or water phase by electrode surface
It is carbon dioxide and water, realizes quick effective removal of pollutant, therefore, electro-catalytic oxidation technology is used for reverse osmosis membrane concentrated water
Treatment has very big technical advantage.But common electro-catalytic oxidation technology there is also some technologies in terms of reverse osmosis membrane concentrated water is processed
Problem, so as to limit its further genralrlization application, is mainly manifested in the following aspects：1) pollutant oxidation removal is not thorough,
Particularly with some macromolecular hardly degraded organic substances, by after open loop, chain rupture, it is difficult to thoroughly by its mineralising, and with pollutant
The reduction of concentration, electrolytic efficiency is remarkably decreased, and energy consumption increase, processing cost is greatly increased；2) during catalytic and oxidative electrolysis technology,
It is carbon dioxide and water that organic pollution is finally mineralized, and produces portion gas, because produced bubble is minimum, is formed with water
Uniformity air-water mixture, and concentrate near pole plate, catalytic and oxidative electrolysis technology unit anode and cathode electrical efficiency is reduced, influence is urged
Change degradation efficiency；3) " concentration polarization " phenomenon is easily produced in polar board surface, as concentration polarization strengthens, electrolytic efficiency declines,
Pollutant removal is deteriorated；4) after long-play, especially salt content sewage higher, the reduction of pole plate resistance tocrocking, amount of scale buildup
Increase, influence system run all right and effluent quality.Therefore, above-mentioned technical problem is urgently solved, is to realize reverse osmosis concentrated water
The key of advanced treating.
The content of the invention
It is anti-it is an object of the invention to provide a kind for the treatment of of intensified by ultrasonic wave electrocatalytic oxidation in order to overcome above-mentioned technical deficiency
The device and method of concentrated water is permeated, reverse osmosis concentrated water is jointly processed by using ultrasonic synergistic electrocatalytic oxidation, can significantly improved
Running efficiency of system and stability, can reduce operating cost again.
The present invention processes the device of reverse osmosis concentrated water for a kind of intensified by ultrasonic wave electrocatalytic oxidation, and the device is included outside tubular
Shell, the top of cylindrical case is provided with delivery port, and bottom is provided with water inlet and ring diversion plate, and described water inlet is located at ring
The top of shape deflector, ring diversion plate inner side forms settling zone, and outside forms guiding region, spoil disposal is provided with below settling zone
Mouthful, reinforcing electrocatalytic oxidation system is provided with cylindrical case around central shaft, if described reinforcing electrocatalytic oxidation system by
Dry catalytic and oxidative electrolysis technology unit and ultrasonic wave generating unit are alternately arranged composition, and catalytic and oxidative electrolysis technology unit and ultrasonic wave occur
The number of unit >=4, depending on particular number is according to reverse osmosis membrane concentrated water water, water quality；
Described catalytic and oxidative electrolysis technology unit is made up of center cylindricality anode and telescopic negative electrode, catalytic and oxidative electrolysis technology unit
Exported by power control system control electric current, voltage and ultrasonic power with ultrasonic wave generating unit；
Wherein described settling zone is separated by ring diversion plate with catalytic and oxidative electrolysis technology unit, settling zone bucket and level
Angle is not less than 40 DEG C.
In device of the present invention, described center cylindricality anode is preferably modified electrode, and electrode is with Titanium
Base material, by nickel, manganese, platinum, palladium one or more of which material composition coating solution, by dipping, roasting technique be obtained；Described
Telescopic negative electrode is preferably high purity metal titanium-based material.
Present invention also offers a kind of method that intensified by ultrasonic wave electrocatalytic oxidation processes reverse osmosis concentrated water, the method bag
Include：Reverse osmosis concentrated water is processed using combined treatment device of the present invention, reverse osmosis concentrated water is entered by water inlet, by water conservancy diversion
Plate enters reinforcing electrocatalytic oxidation system by bottom, by power control system for reinforcing electrocatalytic oxidation system provides direct current
Source, a reinforcing electrocatalytic oxidation system water outlet part is discharged by delivery port, and a part is recycled to reactor bottom and mixes with water inlet
Intensified electrolysis catalytic oxidation system is again introduced into by guiding region jointly, produces dirty slag to realize muddy water by settling zone in electrolytic process
Separate, dirty slag is discharged by mud discharging mouth；Wherein reverse osmosis concentrated water reaction time in device is controlled in 20min~40min.
Method of the present invention, wherein described catalytic and oxidative electrolysis technology unit is in power control system output current condition
Under, reverse osmosis concentrated water is promoted to top from electrocatalytic oxidation unit bottom, realizes that reverse osmosis concentrated water, in device inner loop, is followed
Ring multiplying power is with power control system output current size variation.
Method of the present invention, wherein described catalytic and oxidative electrolysis technology unit loading power supply is dc source, it is preferably electric
Flow in 0~300A, it is adjustable with specific reference to reverse osmosis membrane concentrated water water quality；The described preferred power output of ultrasonic wave generating unit is
100w~1000w, output frequency is 20KHz~40KHz, adjustable with specific reference to reverse osmosis concentrated water water quality.
Compared with prior art, the present invention has following technical characterstic：
1st, using unique electrocatalytic oxidation system design, catalytic and oxidative electrolysis technology unit is in external dc power supply bar for the present invention
Under part, concentrated water is promoted to top by electrolytic catalysis unit bottom, so as to realize that concentrated water is circulated in electrocatalytic oxidation internal system, and
According to impressed current size, control concentrated water makes pollutant obtain repeatedly fully exhaustive oxidation, reinforcing electricity in system interior circulation multiplying power
Catalytic oxidation system contaminant removal efficiency.
2nd, the present invention is installed by by ultrasonic wave generating unit and catalytic and oxidative electrolysis technology units alternately, in ul-trasonic irradiation
Under, macromolecular hardly degraded organic substance molecular structure will change, and promote its chemical bond mechanical oscillation and breakdown rate, help
In the removal of further deep oxidation.Additionally, under ul-trasonic irradiation, by pole plate catalytic action, promoting electrocatalytic oxidation system
More hydroxyl radical free radicals are produced, electrocatalytic oxidation system contaminant removal capacity and speed is significantly improved.
3rd, the carbon dioxide and portion gas produced in electrolytic process are attached to polar board surface in micro-bubble form, pass through
Ultrasonic cavitation effect, can form high temperature, hyperbaric environment around micro-bubble, promote hardly degraded organic substance chemical bond rupture and
Degradation rate, so as to cooperate with catalytic and oxidative electrolysis technology system further to improve the device oxidation efficiency, saves operation energy consumption.
4th, under ul-trasonic irradiation, the electrocatalytic oxidation system Inner electrolysis matter uniformity is remarkably improved, makes polar board surface dirty
Dye thing quickly spreads, and slows down polar board surface " concentration polarization " phenomenon, improves electrolytic efficiency, and by ultrasonic wave cleaning action,
Polar board surface pollutant can further be removed, the pole plate dirty slag that comes off realizes mud-water separation in settling zone, it is to avoid be recirculated to
In catalytic and oxidative electrolysis technology unit, so as to further improve effluent quality.
Brief description of the drawings
Fig. 1 is a kind of structural representation of the device of intensified by ultrasonic wave electrocatalytic oxidation treatment reverse osmosis concentrated water of the invention.
Fig. 2 is the schematic top plan view of the device of Fig. 1.
Wherein, 1, cylindrical case；2nd, delivery port；3rd, water inlet；4th, ring diversion plate；5th, settling zone；6th, guiding region；7th, arrange
Mud mouthful；8th, electrocatalytic oxidation system is strengthened；9th, catalytic and oxidative electrolysis technology unit；10th, ultrasonic wave generating unit；11st, center cylindricality sun
Pole；12nd, telescopic negative electrode；13 power control systems.
Specific embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further described.
Fig. 1-2 provides the device that a kind of intensified by ultrasonic wave electrocatalytic oxidation of the invention processes reverse osmosis concentrated water, the device
Including cylindrical case 1, reinforcing electrocatalytic oxidation system 8, settling zone 5, water inlet 3, ring diversion plate 4, delivery port 2, guiding region
6th, mud discharging mouth 7 and power control system 13；Reverse osmosis concentrated water is entered by water inlet 3, and reinforcing electricity is entered by bottom by guiding region 6
Catalytic oxidation system 8, by power control system 13 for reinforcing electrocatalytic oxidation system 8 provides dc source, strengthens electrocatalytic oxidation
The water outlet of change system 8 part is discharged by delivery port 2, and a part is recycled to reactor bottom and mixes common by guiding region 6 with water inlet
Be again introduced into reinforcing electrocatalytic oxidation system 8, produce dirty slag to realize mud-water separation by settling zone 5 in electrolytic process, dirty slag by
Mud discharging mouth 7 is discharged.
As illustrated, reinforcing electrocatalytic oxidation system 8 is by several catalytic and oxidative electrolysis technology units 9 and ultrasonic wave generating unit
10 are alternately arranged composition (embodiment is 4 in figure), and reverse osmosis concentrated water reaction time in device is controlled in 20min~40min,
Catalytic and oxidative electrolysis technology unit 9 and the particular number of ultrasonic wave generating unit 10 and reaction time are according to reverse osmosis concentrated water water, water quality
Depending on.
Under the conditions of the output current of power control system 13, reverse osmosis concentrated water is from electricity for described catalytic and oxidative electrolysis technology unit 9
Solution catalytic oxidation unit 9 bottom is promoted to top, realizes reverse osmosis concentrated water in device inner loop, and circulating ratio is with power supply control
The output current size variation of system processed 13.
Described catalytic and oxidative electrolysis technology unit 9 is made up of center cylindricality anode 11 and telescopic negative electrode 12, electrolytic catalysis oxygen
Change unit 9 and ultrasonic wave generating unit 10 to be exported by the control electric current of power control system 13, voltage and ultrasonic power.
Described settling zone 5 is separated by ring diversion plate 4 with catalytic and oxidative electrolysis technology unit 9, settling zone bucket and level
Angle is not less than 40 DEG C.
Described center cylindricality anode 11 is modified electrode, electrode with Titanium as base material, by nickel, manganese, platinum, palladium wherein
The coating solution of kind or many kinds of substance composition, is obtained by dipping, roasting technique；Described telescopic negative electrode 12 is high purity metal
Titanium-based material.
The described loading of catalytic and oxidative electrolysis technology unit 9 power supply is dc source, electric current in 0~300A, with specific reference to reverse osmosis
Permeable membrane concentrated water water quality is adjustable；The described power output of ultrasonic wave generating unit 10 is 100w~1000w, and output frequency is 20KHz
~40KHz, it is adjustable with specific reference to reverse osmosis concentrated water water quality.
Embodiment one：
Zhanjiang, Guangdong Province petro-chemical corporation is used for Treated sewage reusing using counter-infiltration system advanced treating secondary bio-chemical effluent,
Feed water by reverse osmosis derives from front end secondary biochemical treatment, and reverse osmosis membrane concentrated water is about 120m3/ d, salt content is high in film concentrated water, and
Containing a large amount of hardly degraded organic substance materials, such as phenyl ring and chelate structure pollutant, it is difficult to contentedly using common biochemical treatment
Square discharge standard.
Using the device and method of intensified by ultrasonic wave electrocatalytic oxidation of the present invention treatment reverse osmosis concentrated water to the said firm's reverse osmosis
Permeable membrane concentrated water has carried out 6m3The 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, and dc source output current is 200A, and ultrasonic power output is 300W,
Frequency is 25KHz, and after being processed through apparatus of the present invention, between 36~47mg/L, average out to 41mg/L, COD averagely goes water outlet COD
Except rate reaches 79%, water outlet meets manufacturer's discharge standard.
Embodiment two：
Ningbo City, Zhejiang Province petro-chemical corporation processes secondary biochemical effluent, counter-infiltration using filtration-reverse osmosis system depth
Producing water is used for plant area's circulating cooling make-up water, and reverse osmosis membrane concentrated water is about 960m3/ d, contains a large amount of difficult degradation ring class materials in film concentrated water
And salt content is higher, it is difficult to meet processing requirement using traditional chemical oxidation and biologic treating technique, factory building is intended to reverse osmosis membrane
Concentrated water treatment technology carries out upgrading.
Using the device and method of intensified by ultrasonic wave electrocatalytic oxidation of the present invention treatment reverse osmosis concentrated water to the said firm's reverse osmosis
Permeable membrane concentrated water has carried out 12m3The 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, and dc source output current is 300A, and ultrasonic power output is 600W,
Frequency is 35KHz, and after being processed through apparatus of the present invention, between 58~72mg/L, average out to 62mg/L, COD averagely goes water outlet COD
Except rate reaches 72%, effluent quality meets manufacturer's regulation requirement.
Claims (4)
1. a kind of intensified by ultrasonic wave electrocatalytic oxidation processes the device of reverse osmosis concentrated water, it is characterised in that including cylindrical case
(1), cylindrical case (1) top is provided with delivery port (2), and bottom is disposed with water inlet (3) and ring diversion plate (4), institute
The water inlet (3) stated forms settling zone (5) positioned at the top of ring diversion plate (4), ring diversion plate (4) inner side, and outside is formed
Guiding region (6), is provided with mud discharging mouth (7) below settling zone (5), reinforcing electricity is provided with around cylindrical case (1) interior central shaft
Catalytic oxidation system (8), described reinforcing electrocatalytic oxidation system (8) is by several catalytic and oxidative electrolysis technology units (9) and ultrasound
Ripple generating unit (10) is alternately arranged composition, the number of catalytic and oxidative electrolysis technology unit (9) and ultrasonic wave generating unit (10) >=
4, depending on particular number is according to reverse osmosis membrane concentrated water water, water quality；
Described catalytic and oxidative electrolysis technology unit (9) is made up of center cylindricality anode (11) and telescopic negative electrode (12), electrolytic catalysis
Oxidation unit (9) and ultrasonic wave generating unit (10) are defeated by power control system (13) control electric current, voltage and ultrasonic power
Go out；
Wherein described settling zone (5) is separated by ring diversion plate (4) with catalytic and oxidative electrolysis technology unit (9), settling zone (5) mud
Bucket is not less than 40 DEG C with level angle.
2. device according to claim 1, it is characterised in that：Described center cylindricality anode (11) is modified electrode, electricity
Pole with Titanium as base material, by nickel, manganese, platinum, palladium one or more of which material composition coating solution, by dipping, roasting work
Skill is obtained；Described telescopic negative electrode (12) is high purity metal titanium-based material.
3. a kind of method that intensified by ultrasonic wave electrocatalytic oxidation processes reverse osmosis concentrated water, it is characterised in that including：Will using right
The device described in 1 is asked to process reverse osmosis concentrated water, reverse osmosis concentrated water is entered by water inlet (3), is entered by bottom by guiding region (6)
Reinforcing electrocatalytic oxidation system (8), by power control system (13) for reinforcing electrocatalytic oxidation system (8) provides dc source,
Reinforcing electrocatalytic oxidation system (8) water outlet part is discharged by delivery port (2), and it is mixed with water inlet that a part is recycled to reactor bottom
Amount to and be again introduced into reinforcing electrocatalytic oxidation system (8) with by guiding region (6), produce dirty slag to pass through settling zone in electrolytic process
(5) mud-water separation is realized, dirty slag is discharged by mud discharging mouth (7)；
Wherein reverse osmosis concentrated water reaction time in device is controlled in 20min~40min.
4. method according to claim 3, it is characterised in that：Described catalytic and oxidative electrolysis technology unit (9) loads power supply
Dc source, electric current is adjustable with specific reference to reverse osmosis concentrated water water quality in 0~300A；Described ultrasonic wave generating unit (10) is defeated
Go out power for 100w~1000w, output frequency is 20KHz~40KHz, adjustable with specific reference to reverse osmosis concentrated water water quality.
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| CN105967313B (en) * | 2016-06-21 | 2019-03-05 | 中国海洋石油集团有限公司 | Photoelectrocatalysioxidization oxidization combined treatment device is recycled in a kind of |
| CN109231606B (en) * | 2018-11-24 | 2023-10-20 | 江苏卓博环保科技有限公司 | Advanced treatment and recycling device and method for cotton pulp waste water |
| 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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