CN106830457A - Electrode couples ozone oxidation integral reactor - Google Patents
Electrode couples ozone oxidation integral reactor Download PDFInfo
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- CN106830457A CN106830457A CN201710177803.8A CN201710177803A CN106830457A CN 106830457 A CN106830457 A CN 106830457A CN 201710177803 A CN201710177803 A CN 201710177803A CN 106830457 A CN106830457 A CN 106830457A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims description 120
- 239000003054 catalyst Substances 0.000 claims description 60
- 230000036647 reaction Effects 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 45
- 239000010936 titanium Substances 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011152 fibreglass Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 230000001154 acute effect Effects 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 24
- 238000006385 ozonation reaction Methods 0.000 abstract description 23
- 238000005859 coupling reaction Methods 0.000 abstract description 18
- 230000008878 coupling Effects 0.000 abstract description 14
- 238000010168 coupling process Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 41
- 239000003344 environmental pollutant Substances 0.000 description 31
- 231100000719 pollutant Toxicity 0.000 description 31
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000002585 base Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
It is more particularly to a kind of by electrode technology and the reactor of ozonation technology coupling treatment of sewage water the present invention relates to a kind of sewage-treatment plant.The present invention is realized coupling by electrode technology and ozonation technology in same reactor, there is provided a kind of equipment cost low, parts consume few, the shortcoming of ozone oxidation selectivity can be evaded, ozone oxidation efficiency is greatly improved, ozone usage is reduced, shortens the ozone reaction time, reached effectively treatment bio-chemical effluent and improve the electrode coupling ozone oxidation integral reactor for the treatment of effeciency.
Description
Technical field
The present invention relates to a kind of sewage-treatment plant, more particularly to one kind is by electrode technology and ozonation technology coupling
Manage the reactor of sewage.
Background technology
Ozonation technology is widely applied in water treatment field, such as sterilizing, the industrial wastewater of city water
Advanced treating etc..The current technology is subject to more and more in organic wastewater particularly difficult for biological degradation method for processing organic wastewater
Attention.But due to its oxidation selectivity, ozone utilization rate is low, operating cost is high the problems such as, the popularization of ozonation technology should
With severely limited.Ozone directly can decompose oxidation operation as a kind of strong oxidizer, but it is anti-with organic matter
There should be stronger selectivity, larger molecular organicses are changed into small organic molecule in can only often making waste water, produce hydroxyl certainly
Efficiency by base is relatively low.
Electrochemical method administers waste water and need not typically add oxidant, and equipment is simple, small volume, and sludge quantity is few, post processing
Simply, the commonly known as green oxidation technology of " environment-friendly ".Meanwhile, traditional three-dimensional electrode reactor treatment difficult for biological degradation
Organic wastewater, most electrochemical degradations to carry out organic wastewater under simple DC Electric Field, therefore organic dirt in waste water
Conversion and the removal efficiency for contaminating thing be not high, it is impossible to realizes the conversion of useless Organic substance in water.
The combination of ozonation technology and electrode technology can improve water treatment effect, but prior art is simple
Electrolysis is combined with ozone oxidation, treatment effeciency is low, high cost.Such as the Chinese patent application of Application No. 201510816139.8
" a kind of wastewater treatment equipment and by the device process waste water method ", including ozone generator, 3 D electrode reactor and
D.C. regulated power supply, wherein ozone gas distribution collet is provided with the 3 D electrode reactor, under the ozone gas distribution collet
Side is provided with ozonation aerated head, granule electrode, main electrode is provided with above the ozonation aerated head, in the 3 D electrode reactor
Cavity wall on insertion be provided with waste liquid charging aperture and sample tap.The technical scheme is directly passed through ozone in electrode reactor,
Treatment effeciency to waste water is low, it is impossible to give full play to each self-applying, there is uncertain interference.
Such as " a kind of catalytic ozonation is combined the Chinese patent application of Application No. 201610051298.8 with Electro Sorb
Coking advanced waste treatment system ", the system includes catalytic ozonation reactor, ozone generator, oxygen tank, gas-liquid separation
Device, filter, electric adsorption device, reuse water tank, concentrated water case, product water solenoid valve, concentrated water magnetic valve and connecting pipe；Its
In, by the water inlet of the outlet after biochemical treatment and through the coking chemical waste water after coagulating sedimentation and the catalytic ozonation reactor
Mouth connection；The delivery port of the catalytic ozonation reactor is connected with gas-liquid separation device；The gas-liquid separation device goes out
The mouth of a river is connected with the water inlet of filter；Described filter delivery port is connected with the water inlet of electric adsorption device, Electro Sorb dress
The delivery port put is connected by producing water solenoid valve with reuse water tank, while being connected with concentrated water case by concentrated water magnetic valve.The technology
Catalytic ozonation reactor and electric adsorption device are simple cascade in scheme, each can only successively be played a role, not
Have and play real synergy, thus the shortcoming existed when each individually processing can not be overcome.
If the Chinese invention patent of Patent No. 201310236853.0 is " at a kind of ozone tail gas reinforcing ozone oxidation waste water
The method and device of reason ", the processing unit includes the preelectrolysis unit and ozone oxidation unit of connection, the ozone oxidation unit
Offgas outlet be connected into preelectrolysis unit.The method makes waste water initially enter preelectrolysis unit carries out cell reaction, cell reaction
Waste water afterwards flows into ozone oxidation unit, and being passed through ozone in ozone oxidation unit is reacted, what ozone oxidation unit was produced
Ozone tail gas are aerated in accessing preelectrolysis unit.The technical scheme is same what preelectrolysis unit and ozone oxidation unit were connected
When, and ozone tail gas are passed through preelectrolysis unit, but preelectrolysis unit and ozone oxidation unit are still each other two relatively independent
Device, thus equipment cost is high.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of equipment cost is low, parts consume few, can
Evade the shortcoming of ozone oxidation selectivity, ozone oxidation efficiency be greatly improved, reduce ozone usage, shorten the ozone reaction time,
Reach effectively treatment bio-chemical effluent and improve the electrode coupling ozone oxidation integral reactor for the treatment of effeciency.
In order to achieve the above object, a kind of electrode coupling ozone oxidation integral reactor designed by the present invention, reaction
Device main body is inner hollow, and the chamber structure of outer closures is divided into cell reaction room and ozone reaction inside it by dividing plate
There is spacing between room, and dividing plate and reactor top board and reactor base plate, the reactor ceiling height above dividing plate is less than
Cell reaction ceiling plate and ozone reaction room ceiling height；The connection of reactor top board and cell reaction room side wall above dividing plate
Place is provided with inlet damper, and upper inlet damper is inclined to cell reaction room direction；Water inlet is provided with the top of cell reaction room, electricity
Multi-group electrode plate is provided with solution reative cell, battery lead plate is connected by the wire being arranged in conduit with external power source；Dividing plate bottom
Portion is provided with lower inlet damper, and lower inlet damper is inclined to ozone reaction room direction；Ozone reaction room bottom is provided with aerating system, exposes
Gas system includes air inlet pipe and microporous aeration disc, and air inlet pipe connection ozone source, microporous aeration disc is arranged in air inlet pipe；Ozone is anti-
Answer and gas collection cap is provided with the top of room, gas collection cap is upside down funnel shape, gas collection cap top passes through blast pipe and tail
Gas breaking plant is connected；Ozone reaction room side wall below gas collection cap is provided with delivery port, and delivery port is effluent weir form.
Preferably, the upper inlet damper is 20 ° -80 ° with the angle of horizontal plane.
Preferably, the lower inlet damper is 90 ° -165 ° with the angle of horizontal plane.
Preferably, the battery lead plate is fixed on electrolytic reaction chamber by draw-in groove；In order to be insulated with reactor, and keep away
Exempt from electrolytic process to be corroded, draw-in groove uses fiberglass, polytetrafluoroethylene (PTFE) or UPVC materials；The positive plate of battery lead plate is used to be had
The titanium plate of the rare earth element coating such as ruthenium, iridium, tantalum, minus plate can be using materials such as titanium plate, graphite cake or stainless steel plates.
Preferably, the battery lead plate spacing is 1-500cm, electrode plate thickness is 1-5mm, and electrode group number is 1-10 groups.
Preferably, delivery port is less than gas collection cap bottom 10-100cm.
Preferably, being passed through powdered catalytic materials in reactor, electrode coupling catalytic ozonation reaction is carried out, can
Using fixed bed form or fluid bed form；Described powdered catalytic materials, its active component is to ozone oxidation and electrolysis
Reaction is respectively provided with catalytic performance, belongs to multiple-effect catalyst.
The reactor of the fixed bed form carries out following Curve guide impeller：Also set up on cell reaction ceiling plate into water stirring
Device, cell reaction room bottom also sets up submersible agitator, and the top sidewall of cell reaction room is provided with water inlet；Battery lead plate bottom
Support net is also set up, support places catalyst solid bed on the net；Ozone reaction ceiling portion gas collection cap is changed to three phase separator,
Three phase separator is upside down funnel shape, and three phase separator top is connected by blast pipe with tail gas breaking plant；Micro-pore aeration
Support net is also set up above disk, support places catalyst solid bed on the net, and fixed bed lower floor is big particle diameter gravel, in fixed bed
Upper strata is catalyst；Ozone reaction room side wall above three phase separator bottom is provided with delivery port, and delivery port is effluent weir shape
Formula.
Used as further preferred, the spacing of the battery lead plate is 100-500cm, and electrode plate thickness is 1-5mm, electrode group number
It is 1-2 groups；The mesh diameter of support net is 1-2mm in cell reaction room, and the catalyst in fixed bed is spherical, and its particle diameter is 3-
5mm, catalyst fixed bed compactedness is 30%-80%；The stir speed (S.S.) of water inlet agitator is 60-500rad/min, and diving is stirred
The stirring intensity for mixing device is 1-10w/m3；Support net uses titanium alloy material in ozone reaction room, and mesh diameter is 5-10mm, gravel
Stone particle diameter is 12-30mm, and catalyst is spherical, and its particle diameter is 3-5mm；Effluent weir crest of weir bottom level is higher than three phase separator bottom
5 ~ 50cm of portion；Described catalyst, is with γ-Al2O3It is carrier, one or more oxygen in load Zn, Ti, Mn, Sn, Fe, Bi
Compound is the catalysis material of active component；Preferably, described γ-Al2O3It is spheroid, a diameter of 3-5mm, active component is
The oxide of Ti, Sn and Mn, active component mol ratio is Ti：Sn：Mn=（10~200）:（1~30）:（5~100）.
The reactor of the fluid bed form carries out following Curve guide impeller：Also set up on cell reaction ceiling plate into water stirring
Device, also sets up submersible agitator in the bottom sidewall of cell reaction room, the top sidewall of cell reaction room is provided with water inlet and urges
Agent adds mouth；Ozone reaction ceiling portion gas collection cap is changed to three phase separator, and three phase separator is upside down funnel shape, outward
Portion is provided with inversion Palta type blade, and three phase separator top is connected by blast pipe with tail gas breaking plant；In three phase separator
Bottom top also sets up inclined-pipe settler, and the ozone reaction room side of same level position is being in inclined-pipe settler bottom
Wall is provided with delivery port, and delivery port is effluent weir form.
Used as further preferred, the dividing plate parallelogram, parallelogram acute angle γ is 45 ° -85 °；Institute
The spacing of battery lead plate is stated for 2-20cm, more preferably 2-6cm, electrode plate thickness is 1-5mm, electrode group number is 2-5 groups；Water inlet is stirred
The stir speed (S.S.) of device is mixed for 60-500rad/min, the stirring intensity of submersible agitator is 1-10w/m3；Delivery port bottom level is high
In three phase separator bottom 5-50cm；The inclined tube inclination angle is 50 ° -70 °；The catalyst for adding, be with Powdered Activated Carbon be carry
Body, one or more oxides in load Zn, Ti, Mn, Sn, Fe, Bi are the catalysis material of active component；Preferably, institute
The Powdered Activated Carbon particle stated is 80-100 mesh, and active component is the oxide of Ti, Sn and Mn, and active component mol ratio is Ti：
Sn：Mn=（10-200）:（1-30）:（5-100）.
The present invention is realized coupling by electrode technology and ozonation technology in same reactor, and operation principle is as follows：It is useless
Water enters in reactor, and tank house is initially entered through upper inlet damper water conservancy diversion, electrode electrolysis oxidation reduction reaction is carried out, by waste water
Middle ring-type, the larger molecular organicses of long-chain carry out open loop, chain rupture, effectively reduce pollutant and are oxidized required chemical energy,
The oxidation efficiency of follow-up ozone oxidation is improved, ozone usage is reduced, while it is selective to solve ozonation technology
Shortcoming；Entered through lower inlet damper water conservancy diversion by the space between dividing plate and reactor base plate through the waste water after first cell reaction
In ozone reaction room, waste water is in the abundant dissolved ozone in ozone reaction room and carries out oxidation reaction, and the waste water containing saturation ozone passes through
Space between dividing plate and reactor top board enters cell reaction room under the water conservancy diversion of upper inlet damper, and the ozone for dissolving saturation exists
Receiving and losing electrons at electrode, carry out rapidly the coupled reaction of electrolysis and ozone oxidation, and waste water is again through lower inlet damper water conservancy diversion weight
New to enter ozone reaction room dissolved ozone, speed up gas and liquid mass transfer rate forms the interior circulation pattern of stabilization, greatly improves ozone profit
Use efficiency；After circulating for several times, gas is discharged outside reactor through gas collection cap and after tail gas breaking plant is destroyed, waste water warp
Effluent weir discharges reactor.The technology is primarily present following reaction mechanism：（1）In ozone reaction room, gaseous ozone is dissolved in useless
In water, ozone molecule direct oxidation pollutant under waste water acid-base condition；（2）Electrode system：High oxidation potential is straight at positive plate
Oxidation stain thing is connect, reduction potential direct-reduction pollutant high at minus plate；（3）Ozone electrode coupled reaction system：Positive plate
The sour environment of surrounding promotes ozone molecule direct oxidation pollutant, and the alkaline environment around minus plate promotes ozone to produce OH
Indirect oxidation pollutant；Ozone molecule obtains electronics and produces O, O3 in negative electrode-Deng intermediate product, indirect oxidation pollutant；Oxygen
Molecule obtains electronics with water reaction generation H in negative electrode2O2, H2O2Can direct oxidation pollutant；H2O2Have with ozone molecule and cooperate with work
With reaction can produce OH.
The reactor of fixed bed form of the present invention is by three-diemsnional electrode technology and catalytic ozonation technical combinations in same anti-
Answer in device, two the series connection applications and coupling application of technology are synchronously realized with fixed bed form；Operation principle is as follows：Waste water enters
Enter in reactor, tank house is initially entered through upper inlet damper and water inlet agitator water conservancy diversion, coordinate the catalyst in fixed bed to enter
The larger molecular organicses of ring-type in waste water, long-chain are carried out open loop, chain rupture, effectively by row three-dimensional electrode electrolysis redox reaction
The pollutant that reduces be oxidized required chemical energy, improve the oxidation efficiency of follow-up ozone oxidation, reduce ozone usage, together
When solve the selective shortcoming of ozonation technology；Through the waste water after first cell reaction submersible agitator plug-flow
Under effect, by the space between dividing plate and reactor base plate through lower inlet damper water conservancy diversion enter ozone reaction room in, waste water and
In fixed bed catalyst is in the abundant dissolved ozone in ozone reaction room and carries out catalytic oxidation, the waste water containing saturation ozone lead to
The space crossed between dividing plate and reactor top board enters cell reaction room under the water conservancy diversion of upper inlet damper, dissolves the ozone of saturation
The receiving and losing electrons at three-diemsnional electrode, carry out rapidly the coupled reaction of three-diemsnional electrode and catalytic ozonation, and waste water is again through lower water inlet
Baffle plate water conservancy diversion reenters ozone reaction room dissolved ozone, and speed up gas and liquid mass transfer rate forms the interior circulation pattern of stabilization, significantly
Improve ozone utilization ratio；Waste water is separated through three phase separator after circulating for several times, and gas discharges reactor through tail gas breaking plant
Outward, catalyst stays in the reaction of reactor interior circulation, and waste water discharges reactor through effluent weir.Added in reactor with fixed bed form
Plus catalyst, compared to two-dimensional electrode, specific surface area, electrode system face body ratio that ozone is contacted with pollutant are greatly improved,
The catalysis efficiency of synergistic activity component, greatly improves reaction efficiency；It is primarily present following reaction mechanism：（1）Ozone catalytic oxygen
Change system, gaseous ozone is dissolved in waste water, ozone molecule direct oxidation pollutant in waste water, pollutant and ozone molecule quilt
Catalyst surface is adsorbed in, the avtive spot of catalyst surface participates in ozone in water decomposition reaction, accelerates ozone decomposed to produce OH
Speed；Pollutant forms the complex compound for easily being reacted with ozone molecule in metal oxide surface；（2）Three-dimensional electrodes system：Sun
High oxidation potential direct oxidation pollutant at pole plate, reduction potential direct-reduction pollutant high at minus plate, catalyst is in electric field
Middle powered because of electrostatic induction, each catalyst granules is respectively formed small galvanic cell, and it is electric that pollutant is adsorbed in catalyst surface
Solution degraded, substantially increases the face body ratio of electrolysis, and current efficiency lifting, energy consumption of reaction declines；（3）Three-diemsnional electrode coupling ozone is urged
Oxidation system：Sour environment around positive plate promotes ozone molecule direct oxidation pollutant, the alkali around minus plate
Property environment promote ozone produce OH indirect oxidation pollutants；Ozone molecule negative electrode and catalyst surface obtain electronics produce O,
O3- wait intermediate product, indirect oxidation pollutant；Oxygen molecule obtains electronics with water reaction generation H in negative electrode2O2, H2O2Can direct oxygen
Change pollutant；H2O2There is synergy with ozone molecule, reaction can produce OH；Catalyst shape under E field electrostatic sensed conditions
Into galvanic cell, the metal oxide of catalyst load is in power on condition and O2Reaction produces OH, pollutant, ozone molecule absorption
In catalyst surface, contacted rapidly with nascent state OH, reaction efficiency is greatly improved（4）Catalyst system：Two kinds of metals of Sn and Ti
Oxide has synergy, and ozone molecule and electric field are using SnO2And TiO2Conduction level differs the characteristic of 0.5V, smelly
Under oxygen and its intermediate product oxidation or under electric field action, TiO2Surface electronic is to SnO2It is mobile, in TiO2Surface forms electronics
Hole, SnO2TiO can be reduced2Surface electronic and hole-recombination probability, hole have extremely strong oxidisability, and Yi Yushui and oxygen are produced
Raw OH.
The reactor of fluid bed form of the present invention is by three-diemsnional electrode technology and catalytic ozonation technical combinations in same anti-
Answer in device, two the series connection applications and coupling application of technology are synchronously realized in fluid bed form；Operation principle is as follows：Waste water enters
Enter in reactor, be subsequently adding fine catalyst, the mixture of waste water and catalyst is through upper inlet damper water conservancy diversion, water inlet agitator
Enter cell reaction room after plug-flow homogeneous, carry out three-dimensional electrolysis redox reaction, ring-type, the macromolecular of long-chain in waste water are had
Machine thing carries out open loop, chain rupture, effectively reduces pollutant and is oxidized required chemical energy, improves the oxidation of follow-up ozone oxidation
Efficiency, reduces ozone usage, while solving the selective shortcoming of ozonation technology；After through first cell reaction,
Under the plug-flow effect of submersible agitator, waste water and fine catalyst under the space warp between dividing plate and reactor base plate by entering
Water baffle plate water conservancy diversion enters in ozone reaction room, waste water and catalyst is in the abundant dissolved ozone in ozone reaction room and carries out catalysis oxidation
Reaction, waste water and catalyst containing saturation ozone pass through water conservancy diversion of the space between dividing plate and reactor top board in upper inlet damper
Lower entrance cell reaction room, dissolve saturation ozone at three-diemsnional electrode receiving and losing electrons, carry out three-diemsnional electrode rapidly and ozone urged
Change the coupled reaction of oxidation, then waste water and catalyst reenter ozone reaction room dissolved ozone through lower inlet damper water conservancy diversion,
Speed up gas and liquid mass transfer rate, forms the interior circulation pattern of stabilization, greatly improves ozone utilization ratio；Waste water after circulating for several times
The separation of fine catalyst, waste water and gas is realized in the presence of three phase separator, gas is anti-through the discharge of tail gas breaking plant
Answer outside device, fine catalyst stay in reactor interior circulation reaction, waste water first pass through inclined-pipe settler precipitation, after by effluent weir
Discharge reactor, secondary solid-liquid point is not carried out in water by the fine catalyst that three phase separator is separate in inclined-pipe settler
From, it is to avoid ensure that water outlet SS is up to standard while catalyst loss.Fine catalyst is fluidizing state form in reactor interior circulation, phase
Than fixed bed, the specific surface area contacted with ozone and pollutant is greatly improved, catalysis efficiency is more；It is primarily present following anti-
Answer mechanism：（1）Catalytic ozonation system, gaseous ozone is dissolved in waste water, ozone molecule direct oxidation pollution in waste water
Thing, pollutant and ozone molecule are adsorbed on catalyst surface, and the avtive spot of catalyst surface participates in ozone in water and decomposes anti-
Should, accelerate ozone decomposed to produce the speed of OH；Pollutant forms the network for easily being reacted with ozone molecule in metal oxide surface
Compound；（2）Three-dimensional electrodes system：High oxidation potential direct oxidation pollutant at positive plate, reduction potential high is direct at minus plate
Also parent pollutant, catalyst is powered because of electrostatic induction in the electric field, and each catalyst granules is respectively formed small galvanic cell, pollution
Thing is adsorbed in catalyst surface by electrolysis and degradation, substantially increases the face body ratio of electrolysis, current efficiency lifting, under energy consumption of reaction
Drop；（3）Three-diemsnional electrode couples catalytic ozonation reaction system：Sour environment around positive plate promotes the direct oxygen of ozone molecule
Change pollutant, the alkaline environment around minus plate promotes ozone to produce OH indirect oxidation pollutants；Ozone molecule is obtained in negative electrode
Electronics produces O, O3 -Deng intermediate product, indirect oxidation pollutant；Oxygen molecule obtains electronics and reacts generation with water in negative electrode
H2O2, H2O2Can direct oxidation pollutant；H2O2There is synergy with ozone molecule, reaction can produce OH；Catalyst is in electricity
Galvanic cell is formed under the conditions of the electrostatic induction of field, the metal oxide of catalyst load is in power on condition and O2Reaction produces OH,
Pollutant, ozone molecule are adsorbed in catalyst surface, are contacted rapidly with nascent state OH, and reaction efficiency is greatly improved.
Brief description of the drawings
Fig. 1 is the structural representation of the embodiment of the present invention 1.
Fig. 2 is the structural representation of the embodiment of the present invention 2.
Fig. 3 is the structural representation of the embodiment of the present invention 3.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1, a kind of electrode coupling ozone oxidation integral reactor of the present embodiment description, reactor body is inside
Hollow, the chamber structure of outer closures, its inside is divided into cell reaction room 2 and ozone reaction room 3, and dividing plate by dividing plate 1
There is spacing between reactor top board and reactor base plate, the reactor ceiling height above dividing plate is less than cell reaction room
Top board and ozone reaction ceiling ceiling height；Reactor top board above dividing plate is provided with the junction of cell reaction room side wall
Inlet damper 4, upper inlet damper is inclined to cell reaction room direction, and upper inlet damper is 20 ° -80 ° with the angle of horizontal plane；Electricity
Water inlet 5 is provided with the top of solution reative cell, electrolytic reaction chamber is provided with multi-group electrode plate 6, and battery lead plate is fixed on electricity by draw-in groove
In solution reative cell, draw-in groove uses fiberglass, polytetrafluoroethylene (PTFE) or UPVC materials；Battery lead plate is by the wire that is arranged in conduit
It is connected with external power source, using the titanium plate with rare earth element coating such as ruthenium, iridium, tantalums, minus plate is used the positive plate of battery lead plate
The materials such as titanium plate, graphite cake or stainless steel plate；Pole plate spacing is 1-500cm, and electrode thickness is 1-5mm, and electrode group number is 1-10
Group；Dividing plate bottom is provided with lower inlet damper 7, and lower inlet damper is to the inclination of ozone reaction room direction, lower inlet damper and horizontal plane
Angle be 90 ° -165 °；Ozone reaction room bottom is provided with aerating system 8, and aerating system includes air inlet pipe and microporous aeration disc,
Air inlet pipe connects ozone source, and microporous aeration disc is arranged in air inlet pipe；Gas collection cap 9, gas are provided with the top of ozone reaction room
Body collecting hood is upside down funnel shape, and gas collection cap top is connected by blast pipe with tail gas breaking plant 10；Gas collection cap
The ozone reaction room side wall of lower section is provided with delivery port 11, and delivery port is effluent weir form, and effluent weir is less than gas collection cap bottom
Portion 10-100cm.
Embodiment 2
As shown in Fig. 2 a kind of electrode coupling ozone oxidation integral type fixed bed reactors of the present embodiment description, reactor body
It is inner hollow, the chamber structure of outer closures, its inside is divided into cell reaction room 2 and ozone reaction room 3 by dividing plate 1,
And there is spacing between dividing plate and reactor top board and reactor base plate, the reactor ceiling height above dividing plate is less than electrolysis
Reative cell top board and ozone reaction ceiling ceiling height；The junction of reactor top board and cell reaction room side wall above dividing plate
It is provided with inlet damper 4, upper inlet damper is inclined to cell reaction room direction, upper inlet damper and the angle of horizontal plane be 20 °-
80°；The top sidewall of cell reaction room is provided with water inlet 5, and cell reaction ceiling plate is provided with into water agitator 6, and electrolysis is anti-
Room bottom sidewall is answered to be provided with submersible agitator 7, the stir speed (S.S.) of agitator of intaking is 60-500rad/min, submersible agitator
Stirring intensity be 1-10w/m3；Electrolytic reaction chamber is provided with multi-group electrode plate 8, and battery lead plate is fixed on cell reaction by draw-in groove
Interior, draw-in groove uses fiberglass, polytetrafluoroethylene (PTFE) or UPVC materials；Battery lead plate is by the wire being arranged in conduit and outside
Power supply is connected, and using the titanium plate with rare earth element coating such as ruthenium, iridium, tantalums, minus plate uses titanium plate, stone to the positive plate of battery lead plate
The material such as black plate or stainless steel plate, pole plate spacing is 100-500cm, and electrode thickness is 1-5mm, and electrode group number is 1-2 groups；Electrode
Plate bottom sets support net, and support places catalyst solid bed 9 on the net, and the mesh diameter of support net is 1-2mm, in fixed bed
Catalyst is spherical, and its particle diameter is 3-5mm, and catalyst fixed bed compactedness is 30%-80%；Dividing plate bottom is provided with lower water inlet gear
Plate 10, lower inlet damper is inclined to ozone reaction room direction, and lower inlet damper is 90 ° -165 ° with the angle of horizontal plane；Ozone is anti-
Room bottom is answered to be provided with aerating system 11, aerating system includes air inlet pipe and microporous aeration disc, and air inlet pipe connection ozone source, micropore exposes
Gas disk is arranged in air inlet pipe；The top of microporous aeration disc sets support net, and support places catalyst solid bed 12 on the net, fixed
Bed lower floor is big particle diameter gravel 13, and fixed bed is at the middle and upper levels catalyst, and support net uses titanium alloy material, and mesh diameter is 5-
10mm, grain size of gravel is 12-30mm, and catalyst is spherical, and its particle diameter is 3-5mm；Ozone reaction ceiling portion is provided with three phase separation
Device 14, three phase separator is upside down funnel shape, and three phase separator top is connected by blast pipe with tail gas breaking plant 15；Three
Ozone reaction room side wall above phase separator bottom is provided with delivery port 16, and delivery port is effluent weir form, effluent weir crest of weir
Bottom level is higher than 5 ~ 50cm of three phase separator bottom.Catalyst in the cell reaction room and ozone reaction room is with diameter
It is the spheroid γ-Al of 3-5mm2O3It is carrier, load Ti, Sn and Mn oxide are the catalysis material of active component, activearm centimorgan
You are than being Ti：Sn：Mn=（10~200）:（1~30）:（5~100）.
Embodiment 3
As shown in figure 3, a kind of electrode coupling ozone oxidation all-in-one fluidization bed reactor of the present embodiment description, reactor body
It is inner hollow, the chamber structure of outer closures, its inside is divided into cell reaction room 2 and ozone reaction room 3 by dividing plate 1,
And there is spacing, dividing plate parallelogram, parallelogram acute angle between dividing plate and reactor top board and reactor base plate
Angle γ is 45 ° -85 °；Reactor ceiling height above dividing plate is less than cell reaction ceiling plate and ozone reaction ceiling top board
Highly；Reactor top board above dividing plate and the junction of cell reaction room side wall are provided with inlet damper 4, upper inlet damper to
Cell reaction room direction inclines, and upper inlet damper is 20 ° -80 ° with the angle of horizontal plane；Set in the top sidewall of cell reaction room
There are water inlet 5 and catalyst to add mouth 15, cell reaction ceiling plate is provided with into water agitator 6, cell reaction room bottom sidewall
Submersible agitator 7 is provided with, the stir speed (S.S.) of agitator of intaking is 60-500rad/min, and the stirring intensity of submersible agitator is
1-10w/m3；Electrolytic reaction chamber is provided with multi-group electrode plate 8, and battery lead plate is fixed on electrolytic reaction chamber by draw-in groove, and draw-in groove is adopted
With fiberglass, polytetrafluoroethylene (PTFE) or UPVC materials；Battery lead plate is connected by the wire being arranged in conduit with external power source, electricity
The positive plate of pole plate uses titanium plate, graphite cake or stainless using the titanium plate with rare earth element coating such as ruthenium, iridium, tantalums, minus plate
The materials such as steel plate, pole plate spacing is 2-6cm, and electrode thickness is 1-5mm, and electrode group number is 2-5 groups；Dividing plate bottom is provided with lower water inlet
Baffle plate 9, lower inlet damper is inclined to ozone reaction room direction, and lower inlet damper is 90 ° -165 ° with the angle of horizontal plane；Ozone
Reative cell bottom is provided with aerating system 10, and aerating system includes air inlet pipe and microporous aeration disc, air inlet pipe connection ozone source, micropore
Aeration plate is arranged in air inlet pipe；Ozone reaction ceiling portion is provided with three phase separator 11, and three phase separator is upside down funnel shape,
Outside is provided with inversion Palta type blade, and three phase separator top is connected by blast pipe with tail gas breaking plant 12；In three-phase separate
Inclined-pipe settler 13 is additionally provided with from device bottom top, inclined tube inclination angle is 50 ° -70 °；It is same being in inclined-pipe settler bottom
The ozone reaction room side wall of one horizontal level is provided with delivery port 14, and delivery port is effluent weir form, and effluent weir bottom level is high
In three phase separator bottom 5-50cm.The catalyst for adding be the Powdered Activated Carbon with 80-100 mesh as carrier, load Ti, Sn and
The oxide of Mn is the catalysis material of active component, and active component mol ratio is Ti：Sn：Mn=（10-200）:（1-30）:（5-
100）.
Claims (10)
1. a kind of electrode couples ozone oxidation integral reactor, it is characterised in that：The reactor body is inner hollow, outward
The chamber structure of portion's closing, cell reaction room and ozone reaction room, and dividing plate and reactor top are divided into inside it by dividing plate
There is spacing between plate and reactor base plate, the reactor ceiling height above dividing plate is less than cell reaction ceiling plate and ozone
Reative cell ceiling height；Reactor top board above dividing plate is provided with inlet damper with the junction of cell reaction room side wall, on
Inlet damper is inclined to cell reaction room direction；Water inlet is provided with the top of cell reaction room, electrolytic reaction chamber is provided with multigroup
Battery lead plate, battery lead plate is connected by the wire being arranged in conduit with external power source；Dividing plate bottom is provided with lower inlet damper, under
Inlet damper is inclined to ozone reaction room direction；Ozone reaction room bottom is provided with aerating system, aerating system include air inlet pipe and
Microporous aeration disc, air inlet pipe connection ozone source, microporous aeration disc is arranged in air inlet pipe；Ozone reaction is provided with gas at the top of room
Collecting hood, gas collection cap is upside down funnel shape, and gas collection cap top is connected by blast pipe with tail gas breaking plant；Gas
Ozone reaction room side wall below collecting hood is provided with delivery port, and delivery port is effluent weir form.
2. a kind of electrode according to claim 1 couples ozone oxidation integral reactor, it is characterised in that：It is described enterprising
Water baffle plate is 20 ° -80 ° with the angle of horizontal plane.
3. a kind of electrode according to claim 1 couples ozone oxidation integral reactor, it is characterised in that：Enter under described
Water baffle plate is 90 ° -165 ° with the angle of horizontal plane.
4. a kind of electrode according to claim 1 couples ozone oxidation integral reactor, it is characterised in that：The electrode
Plate is fixed on electrolytic reaction chamber by draw-in groove, and draw-in groove is made up of fiberglass, polytetrafluoroethylene (PTFE) or UPVC materials；The sun of battery lead plate
Pole plate is made up of the titanium plate with the rare earth element coating such as ruthenium, iridium, tantalum, and minus plate is made up of titanium plate, graphite cake or stainless steel plate.
5. a kind of electrode according to claim 1 or 4 couples ozone oxidation integral reactor, it is characterised in that：It is described
Battery lead plate spacing is 1-500cm, and electrode plate thickness is 1-5mm, and electrode group number is 1-10 groups.
6. a kind of electrode according to claim 1 couples ozone oxidation integral reactor, it is characterised in that：The water outlet
Mouth is less than gas collection cap bottom 10-100cm.
7. a kind of electrode according to claim 1 or 2 or 3 or 4 couples ozone oxidation integral reactor, and its feature exists
In：Also set up on the cell reaction ceiling plate into water agitator, cell reaction room bottom also sets up submersible agitator, electrolysis is anti-
The top sidewall of room is answered to be provided with water inlet；Battery lead plate bottom also sets up support net, and support places catalyst solid bed on the net；It is smelly
Oxygen reative cell top gas collecting hood is changed to three phase separator, and three phase separator is upside down funnel shape, three phase separator top
It is connected with tail gas breaking plant by blast pipe；Support net is also set up above microporous aeration disc, support places catalyst on the net
Solid Bed, fixed bed lower floor is big particle diameter gravel, and fixed bed is at the middle and upper levels catalyst；Ozone above three phase separator bottom is anti-
Room side wall is answered to be provided with delivery port, delivery port is effluent weir form.
8. a kind of electrode according to claim 7 couples ozone oxidation integral reactor, it is characterised in that：The electrode
The spacing of plate is 100-500cm, and electrode plate thickness is 1-5mm, and electrode group number is 1-2 groups；The net of support net in cell reaction room
Bore dia is 1-2mm, and the catalyst in fixed bed is spherical, and its particle diameter is 3-5mm, and catalyst fixed bed compactedness is 30%-
80%；The stir speed (S.S.) of water inlet agitator is 60-500rad/min, and the stirring intensity of submersible agitator is 1-10w/m3；Ozone is anti-
It is 5-10mm into, mesh diameter by titanium alloy material texture to answer in room support net, and grain size of gravel is 12-30mm, catalyst be it is spherical,
Its particle diameter is 3-5mm；Effluent weir crest of weir bottom level is higher than 5 ~ 50cm of three phase separator bottom；The cell reaction room and ozone
Catalyst in reative cell, by with γ-Al2O3It is carrier, one or more oxides in load Zn, Ti, Mn, Sn, Fe, Bi
For the catalysis material of active component is constituted.
9. a kind of electrode according to claim 1 or 2 or 3 or 4 couples ozone oxidation integral reactor, and its feature exists
In：Also set up on cell reaction ceiling plate into water agitator, submersible agitator is also set up in the bottom sidewall of cell reaction room, be electrolysed
The top sidewall of reative cell is provided with water inlet and catalyst adds mouth；Ozone reaction ceiling portion gas collection cap is changed to three-phase separate
From device, three phase separator is upside down funnel shape, and outside is provided with inversion Palta type blade, and three phase separator top passes through blast pipe
It is connected with tail gas breaking plant；Also set up inclined-pipe settler above three phase separator bottom, with inclined-pipe settler bottom
The ozone reaction room side wall that portion is in same level position is provided with delivery port, and delivery port is effluent weir form.
10. a kind of electrode according to claim 9 couples ozone oxidation integral reactor, it is characterised in that：It is described every
Plate parallelogram, parallelogram acute angle γ is 45 ° -85 °；The spacing of the battery lead plate is 2-20cm, battery lead plate
Thickness is 1-5mm, and electrode group number is 2-5 groups；The stir speed (S.S.) of water inlet agitator is 60-500rad/min, submersible agitator
Stirring intensity is 1-10w/m3；Delivery port bottom level is higher than three phase separator bottom 5-50cm；The inclined tube inclination angle be 50 °-
70°；The catalyst for adding, by with Powdered Activated Carbon as carrier, one or more in load Zn, Ti, Mn, Sn, Fe, Bi are aoxidized
Thing is constituted for the catalysis material of active component.
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| CN109775896A (en) * | 2019-03-20 | 2019-05-21 | 南京大学 | A kind of device and method of catalytic ozonation coupling coagulating sedimentation deep purifying biochemical tail water |
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