CN207861965U - A kind of multistage out-phase three-dimensional electrochemical reaction unit for waste water treatment - Google Patents

Abstract

The utility model discloses a kind of multistage out-phase three-dimensional electrochemical reaction units for waste water treatment, the device is multi-stage series system, every section includes at least two reative cells separated by intermediate bulkhead and a gas distribution deslagging chamber, the electrode plate of vertical parallel arrangement is provided in reative cell, electrode plate is alternately anode and cathode, is connected in parallel on external power supply.The granule electrode of supported catalyst is filled between electrode plate.Aeration board, pipe or disk are set in gas distribution deslagging chamber, external gas generator is connected by gas pipeline, oxidizing gas is provided into reactor.Gas distribution deslagging chamber lower end is equipped with evacuation port, periodically carries out body refuse cleaning and the emptying of sewage.The connection of water phase is realized between each reative cell by the gas distribution deslagging chamber of lower end, realizes the unicom of water phase between each section of reactor by overflow port.The utility model structural reduction and integration, easy to operation, maintenance and automation control, sewage treating efficiency are high, few without adding chemical agent, sludge output.

Description

A kind of multistage out-phase three-dimensional electrochemical reaction unit for waste water treatment

Technical field

The utility model belongs to technical field of sewage, is related to a kind of multistage out-phase three-dimensional electrochemical reaction unit.

Background technology

The governing problem of a large amount of high concentrations domestic at present and indegradable industrial effluent becomes environmental area weight urgently to be resolved hurrily Big project, these industrial wastewater organic concentrations are high, and biodegradability is poor, complicated component, contain biological intoxicating substance, traditional object Change and biochemical processing method has larger limitation.

Three-dimensional electrochemical technology is a kind of novel high-level oxidation technology, is filled out in traditional two-dimentional electrochemical reactor Granule electrode composition is filled, has treatment effeciency high, hydraulic detention time is short, and floor space is few, and waste residue is few, and wide spectrum adaptability etc. is excellent Point, has broad application prospects, and becomes at present one of the research hotspot in contamination control field both at home and abroad.The work of three-dimensional electrochemical Include directly effect and indirectly-acting with mechanism.Directly effect is the electrochemical oxidation carried out in electrode surface and reduction reaction, Electrode surface had both included negative and positive major electrode surface, also included all granule electrode surfaces.Numerous granule electrodes greatly increase The contact area of solution and electrode shortens mass transfer distance, improves current efficiency and contaminant degradation effect.

Indirectly-acting refers to the free chain reaction caused in electric field, by oxygen, anode and the particle of aeration dissolving The oxygen that electrode anode end generates generates oxidisability extremely strong hydrogen peroxide and hydroxyl certainly in cathode and the reduction of granule electrode cathode terminal By base, while under the action of electromagnetic field and redox electronics are to catalyst in system again, it is extremely strong to generate a large amount of oxidisability Free radical, HO₂ ^-, O, H, O₂ ^-·, O₃ ^-Deng.These free radicals are reacted with useless Organic substance in water, are generated unstable Organic matter free radical R etc., to cause a large amount of free chain reaction, to which gradually exhaustive oxidation divides by organic pollution Solution is CO₂And H₂O。

The practical engineering application of three-dimensional electrochemical technology is also seldom at present, and equipment investment is high, and operating cost is high, without maturation Equipment and technique.It also needs in reaction unit structure, granule electrode material character, urge with three-dimensional electrochemical technology on a large scale Agent type property, operation process condition etc. carry out a large amount of basic research work and engineering practice.

Utility model content

The purpose of this utility model be in view of the deficiencies of the prior art and a kind of structural reduction, easy to operate, easy for providing In safeguarding and automation control, treatment effeciency is high, without adding the multistage out-phase that any chemical agent, sludge output are few, efficient Three-dimensional electrochemical reaction unit.

To achieve the above object, the utility model uses following technical scheme：

A kind of multistage out-phase three-dimensional electrochemical reaction unit for waste water treatment, feature is that the device includes：It is ontology, outer Power supply and external gas generator are set, water inlet is arranged in the ontology front end, and end is arranged water outlet, is inside at least arranged two sections Reactor, each section of reactor are in series and realize the unicom of water phase between adjacent section reactor by overflow port, wherein：

Every section of reactor is divided at least two reative cells by intermediate bulkhead, and is realized instead by the gas distribution deslagging chamber of lower end Answer the unicom of water phase between room；The electrode plate of two pieces of vertical parallel arrangements is at least arranged in each reative cell, and each reative cell electrode plate is just Pole and cathode are arranged alternately, and are connected in parallel external power supply；Particle filled composite electrode between electrode plate, granule electrode are placed in sieve pore Filler basket in or be stacked on the orifice plate of reative cell bottom；It is equipped with aeration board, pipe or disk in gas distribution deslagging chamber, passes through flue Road connects external gas generator, and every section of reactor lower end is equipped with evacuation port.

The electrode plate is boron-doped diamond film pole plate（BDD）, titanium-based transition metal oxide coated electrode（DSA）、 One kind in stainless steel polar plate, graphite electrode plate or alloy pole plate.Preferably, anode uses boron-doped diamond thin-film electrode（BDD）、 Titanium-based transition metal oxide coated electrode（DSA）In one kind；Cathode is using one kind in stainless steel electrode, graphite electrode.

For the granule electrode using particle as matrix, load thereon is useful for the catalysis of heterocatalysis contaminant degradation and removal Agent；Described matrix be granular activated carbon, alundum (Al2O3) particle or zeolite granular, be used alone or two kinds or it is several mixing make With；Catalyst is titanium dioxide, metal or the mixing of transition metal oxide one or several kinds.Preferably, granule electrode is using work Property charcoal particle or active carbon particle doped alumina particle be matrix, matrix load nano-titanium dioxide, Mn oxide, copper Oxide, ferriferous oxide, ru oxide, palladium oxide, cobalt/cobalt oxide, silver oxide, cerium oxide, titanium oxide, zinc oxidation The one or more of object etc. are granule electrode.

The filler basket horizontally or vertically concatenates to be several.

The external power supply is set as one or several, and every section of reactor is arranged one or several sections of reactors share one.

The gas distribution deslagging chamber is reverse taper or rectangular parallelepiped structure, it is preferred that is designed as rectangular parallelepiped structure, gas distribution deslagging chamber Certain angle of inclination is arranged in bottom, is conducive to the discharge of body refuse and the emptying of sewage.In the gas distribution deslagging chamber be equipped with aeration board, Pipe or disk；Aeration board, pipe or disk connect external gas generator by gas pipeline；

The external gas generator is air compressor or ozone generator.Preferably, it is connected by gas pipeline outer The air compressor or ozone generator set provide compressed air or ozone into reactor.

The evacuation port is for the cleaning of body refuse and the emptying of sewage.

The degradation of organic wastewater with difficult degradation thereby of the utility model for B/C less than 0.3, waste water are entering the utility model dress It is pre-processed before setting, general suspended matter, colloidal impurity and the calcium removed using coagulating sedimentation technology in waste water of pretreatment, Magnesium, phosphorus, metal ion etc. reduce toxic action of these interference factors to catalyst.

The multistage out-phase three-dimensional electrochemical processing of the utility model is that the catalyst for being catalyzed contaminant degradation is supported on grain On sub-electrode, under electric field energy promotion, the pollutant in heterocatalysis degradation water phase is made with directly or indirectly redox With to the oxygenolysis or modified with reduction of complicated organic molecule implementation non-selectivity in sewage, open loop scission of link improves B/ C, while COD is significantly removed, degrade organic amine and ammonia nitrogen.

The beneficial effects of the utility model

1）The utility model has the advantage that for handling organic wastewater with difficult degradation thereby：

A capacity of resisting impact load is strong, and treatment effect is stablized, and effluent quality is excellent；

B management is convenient, modularization reaction unit, complete set technology, and accurately controls, to ensure the stabilization for the treatment of process Operation；

C is compact-sized, operating cost is low.

3）Utility model device can be realized to the efficient process of organic wastewater with difficult degradation thereby, be preserved the ecological environment, difficult drop The improvement of solution organic wastewater solves key technique problem.

Description of the drawings

FIG. 1 is a schematic structural view of the utility model；

Fig. 2 is 2 structural schematic diagram of the utility model embodiment；

Fig. 3 is 3 structural schematic diagram of the utility model embodiment；

Fig. 4 is 4 structural schematic diagram of the utility model embodiment.

Specific implementation mode

The utility model is further described below in conjunction with Figure of description and specific embodiment, but is not therefore limited The scope of protection of the utility model processed.

Refering to fig. 1, the utility model includes by multistage（>=2 sections）The ontology 1 that reactor is composed in series, adjacent section reactor it Between realize water phase unicom overflow port 2, the intermediate bulkhead 3 of separate reactors, by intermediate bulkhead separate reative cell 4, reactor The gas distribution deslagging chamber 5 of lower end, is arranged the electrode plate 6 in two pieces or more vertical parallel arrangements of reative cell, and external power supply 7 is filled out The granule electrode 8 between electrode plate is filled, the bottom orifice plate 10 for banking up granule electrode, the aeration being arranged in gas distribution deslagging chamber Plate, pipe or disk 11, gas pipeline 12 and gas generator 13, the evacuation port 14 of reactor lower end, the water inlet 15 of reaction unit, Water outlet 16.

Embodiment 1

Refering to fig. 1, the present embodiment is set as being sequentially connected in series four sections of reactors, is realized by overflow port 2 between each section of reactor The unicom of flow.Every section of reactor is divided into two isometric reative cells 4 by intermediate bulkhead 3, by anti-between reative cell 4 4 lower end gas distribution deslagging chamber 5 of room is answered to be connected, gas distribution deslagging chamber 5 is designed as inverted pyramidal structures.Each reative cell is arranged two pieces vertically Electrode plate 6 arranged in parallel, electrode plate 6 are connected in parallel external power supply 7.Anode electrode plate uses titanium-based ruthenium iridium electrode, cathode to adopt With pure titanium-matrix electrode.The granule electrode 8 filled between electrode plate loads Nano titanium dioxide, grain using seed activity carbon matrix Sub-electrode 8 is positioned on the porous sieve plate 10 of 4 bottom of reative cell setting.Aeration board 11 is set in gas distribution deslagging chamber 5, passes through gas Pipeline 12 connects external air compressor 13, and compressed air is provided into reactor.Evacuation port 14 is arranged in reactor lower end, uses In the cleaning of body refuse and the emptying of sewage.Water inlet 15 is arranged in reaction unit front end, and water outlet 16 is arranged in rear end.

The present embodiment works in this way：

Multistage out-phase three-dimensional electrochemical reaction unit is for handling high-concentration hardly-degradable（B/C is less than 0.3）Organic wastewater, it is different Mutually catalysis wide spectrum degradable organic pollutant, oxygenolysis or modified with reduction, open loop scission of link improve B/C, while significantly removing COD, degrade organic amine and ammonia nitrogen.Need to carry out preceding processing before sewage enters multistage out-phase three-dimensional electrochemical reaction unit, two Electrochemical coagulation or traditional chemical coagulation are tieed up, suspended matter, colloidal impurity and calcium, magnesium, phosphorus, metal ion in removal waste water etc., Remove certain COD simultaneously.Reaction unit first installs electrode plate, and wiring connects power supply, granule electrode is installed additional in reactor, Power on, the waste water Jing Guo pre-treatment is entered into multistage out-phase three-dimensional electrochemical reaction unit by water inlet 15, waste water enters First reative cell enters the second reative cell by lower porous sieve plate 10 and gas distribution deslagging chamber 5, then by the second reative cell and third The overflow port of reative cell upper end enters third reative cell, and so on, waste water is when flowing through each reative cell, partial contamination substance It is adsorbed on major electrode surface and granule electrode surface, under electric field energy promotion, these pollutants are in anodic-cathodic surface and crowd Multiparticle electrode surface carries out direct oxidation effect and reduction.Meanwhile oxygen, anode and the particle electricity by aeration dissolving The oxygen that pole anode tap generates generates the extremely strong hydrogen peroxide and hydroxyl free of oxidisability in cathode and the reduction of granule electrode cathode terminal Base, at the same again in system electromagnetic field and redox electronics under catalytic action, generating the extremely strong free radical of a large amount of oxidisability, HO₂ ^-, O, H, O₂ ^-·, O₃ ^-Deng.These free radicals are reacted with useless Organic substance in water, generate unstable organic matter certainly By base R etc., to cause a large amount of free chain reaction.Waste water is direct in electrode surface when flowing through each reative cell Under the indirectly-acting of effect and free chain reaction, hardly degraded organic substance therein is gradually degraded, from larger molecular organics Gradually scission of link open loop is degraded to small organic molecule, and partial organic substances are decomposed into CO by exhaustive oxidation₂And H₂O.Final outflow water is from going out The mouth of a river 16 enters subsequent processing or enters discharge bay.

By taking certain chemical Holding Co., Ltd. pyridine insecticides production wastewater treatment as an example, which is high organic matter Content, organic wastewater with high salt, difficult to degrade, the water quality index after coagulating treatment are：CODcr 19110 mg/L, BOD 1146 mg/L, NH₃- N 38.5 mg/L, Cl^-8879 mg/L.After coagulating treatment pyridine insecticides production waste water by Water inlet 15 enters the multistage out-phase three-dimensional electrochemical reaction unit of embodiment 1, and water outlet flows out reaction unit from water outlet 16.Even Continuous Inlet and outlet water, hydraulic detention time 160min, voltage strength 0.5V/cm, after continuous operation 10d, effluent index is：CODcr 3862 mg/L, BOD 686 mg/L, NH₃- N 15 mg/L, Cl^- 1624 mg/L。BOD₅/ COD is improved by 0.06 to 0.18, can Biochemical significantly improves.Water outlet observes active microorganism and protozoan under the microscope after placing 14 days（With infusorian Based on class）.Water outlet is adjusted load and enters subsequent biological treatment device and subsequent desalter.

Embodiment 2

Referring to Fig.2, the present embodiment is set as being sequentially connected in series four sections of reactors, realized by overflow port 2 between each section of reactor The unicom of flow.Every section of reactor is divided into two isometric reative cells 4 by intermediate bulkhead 3, by anti-between reative cell 4 4 lower end gas distribution deslagging chamber 5 of room is answered to be connected, gas distribution deslagging chamber 5 is designed as inverted pyramidal structures.Each reative cell is arranged two pieces vertically Electrode plate 6 arranged in parallel, electrode plate 6 are connected in parallel external power supply 7.Reactor anode electrode plate uses boron-doped diamond film Pole plate（BDD）, cathode is using stainless steel electrode.Granule electrode 8 is using seed activity carbon matrix Supported Manganese oxide, Cu oxide And ferriferous oxide, granule electrode 8 are filled in the filler basket 9 with sieve pore, multiple filler baskets 9 are horizontally or vertically in reative cell 4 Concatenation.Aeration board 11 is set in gas distribution deslagging chamber 5, external air compressor 13 is connected by gas pipeline 12, to reactor Interior offer compressed air.Evacuation port 14 is arranged in reactor lower end, for the cleaning of body refuse and the emptying of sewage.Reaction unit front end Water inlet 15 is set, and water outlet 16 is arranged in rear end.The present embodiment course of work is the same as embodiment 1.

With Hebei Chemical Group carbon lipid（Two formicester of succinic acid；Succinic acid diisopropyl fat；Two formicester of succinyl succinic acid Deng）For producing waste water, the water quality index after coagulating treatment is：CODcr 63252 mg/L, BOD 0 mg/L, Cl^- 135 mg/L.Carbon lipid production waste water after coagulating treatment is entered the three-dimensional electricity of multistage out-phase of embodiment 2 by water inlet 15 Chemical reaction equipment, water outlet flow out reaction unit from water outlet 16.Continuous flow, hydraulic detention time 200min, voltage are strong After degree 1.0V/cm, continuous operation 8d, effluent index is：CODcr 6847 mg/L, BOD 1621 mg/L, Cl^- 19 mg/L。 BOD₅/ COD is improved by 0 to 0.24, and biodegradability significantly improves.Water outlet be adjusted load enter subsequent biological treatment device with And subsequent desalter.

Embodiment 3

Refering to Fig. 3, the present embodiment is set as being sequentially connected in series four sections of reactors, is realized by overflow port 2 between each section of reactor The unicom of flow.Every section of reactor is divided into two isometric reative cells 4 by intermediate bulkhead 3, by anti-between reative cell 4 4 lower end gas distribution deslagging chamber 5 of room is answered to be connected, gas distribution deslagging chamber 5 is designed as rectangular parallelepiped structure.Each reative cell is arranged two pieces vertically Electrode plate 6 arranged in parallel, electrode plate 6 are connected in parallel external power supply 7.Reactor anode electrode plate uses titanium-based ruthenium iridium electrode, Cathode uses graphite electrode.Granule electrode 8 is using seed activity carbon matrix Supported Manganese oxide, Cu oxide, ferriferous oxide, grain Sub-electrode 8 is filled in the filler basket 9 with sieve pore, and multiple filler baskets 9 horizontally or vertically concatenate in reative cell 4.Gas distribution deslagging Aeration board 11 is set in room 5, external ozone generator 13 is connected by gas pipeline 12, it is smelly that compression is provided into reactor Oxygen.Evacuation port 14 is arranged in reactor lower end, for the cleaning of body refuse and the emptying of sewage.Water inlet is arranged in reaction unit front end 15, water outlet 16 is arranged in rear end.The present embodiment course of work is the same as embodiment 1.

By taking triethylamine wastewater treatment as an example.Zeolite synthesis crystallization mother liquor waste water contains all kinds of organic amines, wherein there is representative Property is triethylamine hydrochloride.Such waste water is the waste water of typical high concentration, high salinity and difficult for biological degradation.Have due to lacking The processing means of effect, current this kind of waste water mainly carry out high temperature incineration, and processing cost is high, it is difficult to maintain.In the present embodiment, The water quality index of triethylamine waste water after coagulation pre-treatment is：CODcr 545 mg/L of 46131 mg/L, BOD, triethylamine Concentration 28172 mg/L, Cl^-14605 mg/L.Triethylamine waste water after coagulating treatment enters embodiment 3 by water inlet 15 Multistage out-phase three-dimensional electrochemical reaction unit, water outlet from water outlet 16 flow out reaction unit.Continuous flow, when hydraulic retention Between 200min, after voltage strength 0.8V/cm, continuous operation 15d, effluent index is：CODcr 8863 mg/L, BOD1265 mg/ L, triethylamine 6402 mg/L, Cl^-3934mg/L, COD removal rate 81%, triethylamine removal rate 77%, Cl^-Removal rate 73%, B/C by 0.012 improves to 0.14.Water outlet can enter subsequent biological treatment device and subsequent desalter after being adjusted load.

Embodiment 4

Refering to Fig. 4, the present embodiment is set as being sequentially connected in series four sections of reactors, is realized by overflow port 2 between each section of reactor The unicom of flow.Every section of reactor is divided into two isometric reative cells 4 by intermediate bulkhead 3, by anti-between reative cell 4 4 lower end gas distribution deslagging chamber 5 of room is answered to be connected, gas distribution deslagging chamber 5 is designed as rectangular parallelepiped structure.Each reative cell is arranged two pieces vertically Electrode plate 6 arranged in parallel, electrode plate 6 are connected in parallel external power supply 7.Reactor anode electrode plate uses stainless steel, cathode to adopt Use stainless steel electrode.Granule electrode 8 is using the base activated charcoal particulate load Cu oxides of particle h and ferriferous oxide, granule electrode 8 It is positioned on the porous sieve plate 10 of 4 bottom of reative cell setting.Aeration board 11 is set in gas distribution deslagging chamber 5, passes through gas pipeline 12 External ozone generator 13 is connected, compression ozone is provided into reactor.Evacuation port 14 is arranged in reactor lower end, is used for body refuse Cleaning and sewage emptying.Water inlet 15 is arranged in reaction unit front end, and water outlet 16 is arranged in rear end.The present embodiment course of work With embodiment 1.

By taking the processing of Shandong wastewater of caprolactam production as an example, the water quality index after coagulating treatment is：CODcr 8560mg/L, BOD 220 mg/L, Cl^-7849 mg/L, NH₃-N 7957 mg/L.Waste water after coagulating treatment is by intaking Mouth 15 enters the multistage out-phase three-dimensional electrochemical reaction unit of embodiment 4, and water outlet flows out reaction unit from water outlet 16.Continuously into It is discharged, hydraulic detention time 240min, voltage strength 0.33V/cm, after continuous operation 10d, effluent index is：CODcr 1504 Mg/L, BOD 431 mg/L, Cl^-863 mg/L, NH₃-N 130 mg/L。BOD₅/ COD is improved by 0.03 to 0.29, biochemical Property significantly improves.Water outlet is adjusted load and enters subsequent biological treatment device and subsequent desalter.

The above is only preferred embodiments of the present invention, and the scope of protection of the utility model is simultaneously not only limited to In above-described embodiment.Every technical solution belonged under the utility model thinking belongs to the scope of protection of the utility model.It answers This points out, for those skilled in the art, the improvement under the precursor for not departing from the utility model principle And retouching, these improvements and modifications also should be regarded as the scope of protection of the utility model.

Claims (8)

1. a kind of multistage out-phase three-dimensional electrochemical reaction unit for waste water treatment, which is characterized in that the device includes：Ontology （1）, external power supply（7）And external gas generator（13）, the ontology（1）Water inlet is arranged in front end（15）, end is provided The mouth of a river（16）, second stage reactor is inside at least set, and each section of reactor is in series and passes through overflow port（2）Realize adjacent section reactor Between water phase unicom, wherein：

Every section of reactor is by intermediate bulkhead（3）It is divided at least two reative cells（4）, and the gas distribution deslagging chamber for passing through lower end（5） Realize the unicom of reacting chamber space water phase；Each reative cell（4）The electrode plate of two pieces of vertical parallel arrangements is at least set（6）, each anti- Answer room（4）Electrode plate anode and cathode are arranged alternately, and are connected in parallel external power supply（7）；Electrode plate（6）Between particle filled composite electrode （8）, granule electrode（8）It is placed in the filler basket with sieve pore（9）In or be stacked in reative cell（4）The orifice plate of bottom（10）On；Cloth Gas deslagging chamber（5）It is interior to be equipped with aeration board, pipe or disk（11）, pass through gas pipeline（12）Connect external gas generator（13）, often Section reactor lower end is equipped with evacuation port（14）.

2. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the gas distribution deslagging chamber （5）For reverse taper or rectangular parallelepiped structure.

3. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the electrode plate（6） For boron-doped diamond film pole plate, titanium-based transition metal oxide coated electrode, stainless steel polar plate, graphite electrode plate or alloy pole plate In one kind.

4. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the external power supply （7）It is set as one or several, every section of reactor is arranged one or several sections of reactors share one.

5. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the granule electrode （8）Using particle as matrix, load thereon has catalyst.

6. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the filler basket（9） It is horizontally or vertically concatenated to be several.

7. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the external gas hair Raw device（13）For air compressor or ozone generator.

8. multistage out-phase three-dimensional electrochemical reaction unit according to claim 1, which is characterized in that the evacuation port（14） For the cleaning of body refuse and the emptying of sewage.