CN105236626B

CN105236626B - The multistage light electrolysis Fenton's reaction device and its application method of a kind of module type iron carbon filler

Info

Publication number: CN105236626B
Application number: CN201510607591.3A
Authority: CN
Inventors: 张毅; 赵克强; 王伟; 王伟民; 王霞; 卜元卿; 王娜; 宋宁慧; 唐秋萍; 吴京; 李秀霞
Original assignee: Nanjing Institute of Environmental Sciences MEP
Current assignee: Nanjing Institute of Environmental Sciences MEP
Priority date: 2015-09-22
Filing date: 2015-09-22
Publication date: 2018-03-30
Anticipated expiration: 2035-09-22
Also published as: CN105236626A

Abstract

The invention discloses the multistage light electrolysis Fenton's reaction device and its application method of a kind of module type iron carbon filler, belong to environmentally friendly water treatment field.It includes wastewater influent pump, H₂O₂Throwing device and pipe-line mixer, in addition to light electrolysis Fenton's reaction device, wherein, the intake pump and the H₂O₂Throwing device connects, H₂O₂Throwing device is connected with the pipe-line mixer, pipe-line mixer is connected with the multistage light electrolysis Fenton's reaction device, the multistage light electrolysis Fenton's reaction device appearance is in square, inside is divided into 4 units along opposite side midpoint, wherein there are 2 multistage light electrolysis units, 1 oxidizing, flocculating unit and 1 precipitation unit, 2 multistage light electrolysis units are connected after being connected with oxidizing, flocculating unit, and oxidizing, flocculating unit is connected with precipitation unit.The problem of present invention solves iron carbon filler and is easily passivated, and it is difficult to change, and waste water decoloring is not thorough, solarization air cap easily blocks, flco is not easy to precipitate.

Description

A kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler and its use Method

Technical field

The present invention relates to the purified treatment engineering of such as industry waste water such as printing and dyeing, chemical industry, plating, agricultural chemicals, coking, belong to ring Water conservation process field, and in particular to the multistage light electrolysis-Fenton's reaction device and its application method of a kind of module type iron carbon filler.

Background technology

Iron-carbon micro-electrolysis and Fenton oxidation technology are two kinds of different wastewater processing technologies, and independent use is used equally for highly concentrated Degree, difficult for biological degradation, the treatment of Organic Wastewater of biodegradability difference.

Iron-carbon micro-electrolysis be in acid condition, when waste water fully contacts with iron-carbon micro-electrolysis filler, iron and carbon in waste water Between formed galvanic effect (difference in Electrode Potential 1.2V), electrochemical reaction occurs in the aqueous solution containing acidic electrolyte bath. Nascent state atom [H] and Fe caused by reaction²⁺Etc. can with waste water many components occur redox reaction, can reach makes to give up Water COD reductions, BOD rises, biodegradability (B/C) raising and waste water decoloring and other effects.

Fenton's reaction is under acid conditions of the pH less than 4, by Fe²⁺And H₂O₂Mix to obtain oxidability very strong OH (oxidizing electrode current potential 2.80V), so as to by the reaction of the pollutant oxidation Decomposition in waste water.Be swift in response, oxygen Change does not produce the advantages that secondary pollution more thoroughly,.

In summary, the two is all to be reacted in acid condition, caused Fe during iron-carbon micro-electrolysis²⁺It is Fenton One of major pharmaceutical agent of reaction.For these reasons, gradually there is research that iron-carbon micro-electrolysis and Fenton oxidation technology are incorporated in into one Rise, form a kind of new wastewater treatment high-level oxidation technology --- iron-carbon micro-electrolysis-Fenton oxidation technology.In acid condition, Fe caused by iron-carbon micro-electrolysis reaction²⁺, with adding the H in waste water₂O₂Generation Strong oxdiative reacts, and has reduced Fenton's reaction Fe²⁺Throw Dosage, improve disposal ability of the device to pollutant.

But in actual applications, currently used iron-carbon micro-electrolysis-Fenton's reaction device is primarily present problems with：

1) the conventional iron carbon filler profile that is used is generally spheroidal, granular, annular or strip, typically by physics pressure Synthesis type, do not solidify by high-temperature firing, in use easily softening, Song Hua, be compacted, filler surface is easily de- after longtime running Fall to form passivating film, the suspended particulate such as part iron carbon mud is gradually deposited at the filler surface in bottom, has obstructed filler with giving up Effective contact of water, causes waste water treatment efficiency to reduce.

2) in tradition iron-carbon micro-electrolysis reactor, filler typically uses landfill state, and stack up is not relative during use Fixed structural support, filler size diminishes after long-term operating, and porosity declines between filler；The more heavier mass of upper strata iron content Filler gradually sinks, and causes filler distribution in pond uneven while crushing lower floor's smaller filler, forms cutout or slough, no Waste water fluidised form is only influenceed, light electrolysis effect is influenceed and causes treatment effeciency to decline, also greatly increase follow-up replacement difficulty.I.e. Cleared up whole waste water in emptying reactor, if open-assembly time is longer, it is also possible to whole packing layer is all lumpd, lead Reactor is caused entirely to scrap.

3) in iron-carbon micro-electrolysis-Fenton's reaction device conventional, micro-electrolysis stuffing is stacked upon as one layer, due to Supporting plate limited load bearing capacities, packing layer thickness is typically small, and waste water is after light electrolysis layer, during continuing up plug-flow It can not be in contact again with iron carbon filler, light electrolysis effect is limited.

4) in light electrolysis-Fenton's reaction device conventional, H is added in light electrolysis unit mostly₂O₂After proceed by exposure Gas, a large amount of oxygenations can make Fe²⁺It is converted into Fe³⁺, slow down Fenton's reaction speed, reduce pollutant oxidation effectiveness；But in Fenton oxidation But there is no oxygenic aeration after end, cause Fe in water outlet²⁺It is more, add the Fe (OH) formed after alkali₂Lighter weight is not easy to precipitate, and Due to the Fe of residual in waste water²⁺Colour developing causes chroma in waste water higher, and visual sensory is poor.

5) floccule body formed after Fenton's reactions, because aeration time is longer, flco surface attachment has many micro-bubbles It is not easy to precipitate, conventional precipitation method is ineffective.

Chinese invention patent, publication number：103880225A, publication date：2014.6.25 it is micro- to disclose a kind of multistage iron carbon Electrolysis coupling Fenton oxidation bed reactor, it is characterised in that it include lifting water pump, inlet channel, hydrogen peroxide throwing device, Inlet channel blender, distributing water room, multistage iron-carbon micro-electrolysis couple Fenton oxidation bed reactor body, take material mouth, fe With grain active carbon mixture layer, water outlet settling section, sieve plate water distribution system, mud discharging mouth, reactor outlet canal, outlet pipe and precipitation Pond, sedimentation basin include sedimentation basin body, outlet conduit and spoil disposal pipeline.A kind of multistage iron-carbon micro-electrolysis coupling that the invention is proposed Fenton oxidation bed reactor is closed, solves traditional coking waste water treatment process to difficult degradation complexity organic pollutant removal effect not It is preferable and the problems such as cause COD in water outlet, ammonia nitrogen, total nitrogen and colourity not up to standard, for the difficult degradation in waste water is polycyclic, heterocyclic The processing of organic matter and poisonous and harmful substance is extremely effective.It is disadvantageous in that, 1) hydrogen peroxide throwing device be arranged on into On waterpipe blender so that can not being sufficiently mixed for waste water and hydrogen peroxide, be further unfavorable for mixing liquid more The light electrolysis and Fenton's reaction carried out in level iron-carbon micro-electrolysis coupling Fenton oxidation bed reactor body；2) fe and particle Activated carbon is mixture layer, and after long-term operating, the filler of the more heavier mass of upper strata iron content gradually sinks, and lower floor is smaller fills out for crushing Cause filler distribution in mixture layer uneven while material, not only influence waste water fluidised form, and influence light electrolysis Fenton's reaction Effect, treatment effeciency is caused to decline；3) take material mouth and take material position in the side of fe and grain active carbon mixture layer, change It cannot be guaranteed uniform filling during material, and Waste iron slag will be cleaned out, long-term stack can lump, and form short stream or stagnant water Area, it otherwise can influence light electrolysis Fenton's reaction effect, it is difficult to remove, waste time and energy, take inconvenience；4) added in light electrolysis unit H₂O₂Afterwards, Fe in water outlet is caused²⁺It is more, add the Fe (OH) formed after alkali₂Lighter weight is not easy to precipitate, and due to residual in waste water Fe²⁺Colour developing causes chroma in waste water higher, and visual sensory is poor.

The content of the invention

1. to solve the problems, such as

Easily it is passivated, lumps for filler existing for wastewater treatment in the prior art, dead band Huo Duanliu areas in reactor is present Cause the ineffective phenomenon of light electrolysis Fenton's reaction, the present invention proposes a kind of multistage light electrolysis-sweet smell of module type iron carbon filler Reaction unit and its application method, it is solved the problems, such as, and water treatment effect is poor, color is returned in water outlet, and simple in construction, filler is not Easily passivation, caking, it is convenient that installation is changed, and device Nei Wuduanliu areas, dead band produce, filler Multi-layers distributing, treatment effect in pond It is stable.

2. technical scheme

To solve the above problems, technical scheme provided by the invention is：

A kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler, including wastewater influent pump, H₂O₂Add dress To put and pipe-line mixer, it also includes light electrolysis-Fenton's reaction device, wherein, the wastewater influent pump is arranged on wastewater influent Guan Shang, sewage water inlet pipe and the H₂O₂After throwing device connection, H₂O₂Throwing device connects with the pipe-line mixer, institute The pipe-line mixer stated is connected by pipeline with the light electrolysis-Fenton's reaction device；

The light electrolysis-Fenton's reaction device includes four units, wherein having two light electrolysis units, an oxidizing, flocculating Unit and a precipitation unit, two light electrolysis units connect after being connected with oxidizing, flocculating unit, oxidizing, flocculating unit and precipitation Unit connects, and described precipitation unit side is provided with outlet pipe, and described precipitation unit bottom is provided with discharge pipeline.Micro- electricity Solution-Fenton's reaction device appearance is in square, and inside is equally divided into 4 units along opposite side midpoint；Two light electrolysis units are in parallel, normally One is only used during operation, stoppage in transit opens another unit when safeguarding, it can be ensured that device is continuously run.

Preferably, the H₂O₂Throwing device includes H₂O₂Storage tank, H₂O₂Chemical feed pipe and H₂O₂Dosing pump；Described H₂O₂Storage The bottom of groove and H₂O₂Chemical feed pipe connects, described H₂O₂Chemical feed pipe is provided with H₂O₂Dosing pump.

Preferably, the H₂O₂Vertical line of the chemical feed pipe along sewage water inlet pipe is inserted into the center position of cross section, H₂O₂Add Outlet of the pencil in sewage water inlet pipe, to be cut along water (flow) direction reverse side, cutting face and water (flow) direction be at 45 °~60 ° of angles, expand Big H₂O₂The discharge area of chemical feed pipe, H₂O₂Between opening position and pipe-line mixer that chemical feed pipe connects with sewage water inlet pipe away from From more than 300mm so that H₂O₂It can be well mixed with sewage.

Preferably, the bottom of the light electrolysis unit is provided with discharge pipeline, and discharge pipeline is connected with sludge hopper, set on sludge hopper There is aerator, water-distributing device is provided with above aerator, 3-6 layer micro-electrolysis reaction layers are provided with above water-distributing device, with Increase the time of contact of waste water and filler, it is ensured that micro-electrolysis reaction effect, micro-electrolysis reaction layer top are provided with effluent trough, gone out Tank bottom right side is provided with outlet pipe, where plane where plane, water-distributing device where aerator and micro-electrolysis reaction layer Plane is parallel to each other, and described water-distributing device is connected by pipeline with described pipe-line mixer, in the light electrolysis unit Outlet pipe connects with the center water inlet pipe in oxidizing, flocculating unit.Intake by light electrolysis unit bottom, light electrolysis unit top Effluent trough water outlet, body refuse caused by operation discharge from the discharge pipeline for being arranged on light electrolysis unit bottom.

Preferably, be provided with NaOH automatic medicament feeding systems above the oxidizing, flocculating unit, NaOH automatic medicament feeding systems by NaOH solution storage tank, NaOH chemical feed pipes and NaOH sensing dosing pump compositions, the bottom of described NaOH solution storage tank adds with NaOH Pencil connects, and described NaOH chemical feed pipes are provided with NaOH sensing dosing pumps, and described NaOH chemical feed pipes stretch into center water inlet pipe Interior, center water inlet pipe is arranged on the central axis of oxidizing, flocculating unit, the Upper vertical insertion oxidizing, flocculating of center water inlet pipe PH on-line computing models are provided with effluent trough at the top of unit, in effluent trough, described pH on-line computing models add with NaOH sensings Teat pipette connects, and effluent trough bottom right side is provided with outlet pipe, and center water inlet bottom of the tube is provided with umbrella shape diffuser, oxidizing, flocculating list The bottom of member is provided with aerator, and sludge hopper is provided with below aerator, discharge pipeline is provided with below sludge hopper, described Outlet pipe in oxidizing, flocculating unit connects with the center water inlet pipe in precipitation unit.

Preferably, center water inlet pipe is provided with the central axis of the precipitation unit, center water inlet pipe Upper vertical is inserted Enter in the effluent trough at the top of precipitation unit, the side bottom of effluent trough is connected provided with outlet pipe, and center water inlet pipe is passed through and is arranged on Swash plate in precipitation unit, for the floccule body formed after Fenton's reaction, because aeration time is longer, flco surface attachment has very More micro-bubbles are not easy to precipitate, the ineffective phenomenon of conventional precipitation method；Swash plate is strengthening sedimentation effect；Center water inlet pipe Bottom is provided with umbrella shape diffuser, and precipitation unit bottom is provided with sludge hopper, discharge pipeline is provided with below sludge hopper.

Preferably, described aerator is identical with water-distributing device structure, is made up of main, branch pipe, and branch pipe is symmetrically and evenly Ground is arranged on the both sides of main, and branch pipe is vertical with main, is provided with hole in branch pipe surface, and the hole on branch pipe is hung down with branch pipe cross section Nogata is evenly distributed on vertical line both sides in 45 ° of angles.To prevent that flco or particulate matter block aperture in waste water, aerator Hole is used to be aerated, and the hole of water-distributing device is used for water distribution.

Preferably, the micro-electrolysis reaction layer is made up of supporting plate and module type filler, and mould is set side by side with supporting plate Group formula filler, described module type filler are made up of laminal filter, PVC brackets, and described PVC brackets are cuboid-type, built-in Neck, described laminal filter are inserted vertically into neck, and 600~1800 laminal filters are shared on every layer of micro-electrolysis reaction layer.

Preferably, the center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, bottom length Spend and be shaped as upside-down trapezoid for (1.2~1.5) D, the sludge hopper front view, the spoil disposal pipe diameter is not less than 200mm.

A kind of application method of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler, step are：

A. according to described above, a kind of multistage light electrolysis-Fenton's reaction device of described module type iron carbon filler is built；

B. discharge pipeline is reviewed and validate to be closed；

C. valve, wastewater influent pump and the H closed on an outlet pipe connected with light electrolysis unit₂O₂Dosing pump, make micro- Light electrolysis unit in electrolysis-Fenton's reaction device only has one and can be used in sewage disposal；

D. valve, wastewater influent pump and the H on the outlet pipe that another is connected with light electrolysis unit are opened₂O₂Dosing pump, make Light electrolysis unit in light electrolysis-Fenton's reaction device only has one and can be used in sewage disposal；Open H₂O₂Dosing pump is to sewage Middle addition H₂O₂；Sewage enters sewage water inlet pipe, H through wastewater influent pump₂O₂H in storage tank₂O₂Solution is through H₂O₂Dosing pump, by H₂O₂Chemical feed pipe is from H₂O₂Chemical feed pipe cutting face is flowed out, and into sewage water inlet pipe, is collaborated with sewage, both are at pipe-line mixer It is sufficiently mixed；

The sewage for flowing out pipe-line mixer enters in the water-distributing device in light electrolysis unit, flows into dry on water-distributing device Pipe, flowed out out of hole on branch pipe, as sewage is constantly flowed into light electrolysis unit, water level rise, sewage gradually with it is each Micro-electrolysis reaction layer contacts, and sewage and laminal filter, i.e. iron carbon filler fully contact, and in acid condition, the micro- electricity of iron carbon occurs Solution is reacted, and galvanic effect is formed between iron and carbon in waste water, difference in Electrode Potential 1.2V, is containing the water-soluble of acidic electrolyte bath Electrochemical reaction occurs in liquid, nascent state atom [H] and Fe caused by reaction²⁺Etc. can be aoxidized with many components in waste water Reduction reaction, can reach makes waste water COD reduction, BOD rises, biodegradability (B/C) raising and waste water decoloring and other effects；

The H of addition₂O₂With iron-carbon micro-electrolysis reaction caused by Fe²⁺Mix, under acid conditions of the pH less than 4, Generation Fenton's reaction, the very strong OH of oxidability (oxidizing electrode current potential 2.80V) is obtained, so as to by the pollutant oxygen in waste water Change the reaction decomposed, have the advantages that to be swift in response, aoxidize more thoroughly, do not produce secondary pollution；

In summary, iron-carbon micro-electrolysis reaction and Fenton's reaction are all to be reacted in acid condition, iron-carbon micro-electrolysis During caused Fe²⁺It is one of major pharmaceutical agent of Fenton's reaction, iron-carbon micro-electrolysis and Fenton oxidation technology is combined together, Form a kind of new wastewater treatment high-level oxidation technology --- light electrolysis-Fenton oxidation technology, in acid condition, the micro- electricity of iron carbon Fe caused by solution reaction²⁺, with adding the H in waste water₂O₂Generation Strong oxdiative reacts, and has reduced Fenton's reaction Fe²⁺Dosage, improve Disposal ability of the device to pollutant.

Conventional reactor, does not have oxygenic aeration after Fenton oxidation terminates, causes Fe in water outlet²⁺It is more, add shape after alkali Into Fe (OH)₂Lighter weight is not easy to precipitate, and due to the Fe of residual in waste water²⁺Colour developing causes chroma in waste water higher, visual impression See poor；The present invention was not both aerated directly, also without alkali is added, avoided the generation of above-mentioned two situations.

E. H is added₂O₂After end, the aerator of light electrolysis unit was aerated 10~15 minutes at interval of 45 minutes；And commonly use Light electrolysis-Fenton's reaction device in, add H in light electrolysis unit mostly₂O₂After proceed by aeration, a large amount of oxygenations can make Fe²⁺It is converted into Fe³⁺, and Fe²⁺It is one of major pharmaceutical agent of Fenton's reaction, thus slows down Fenton's reaction speed, reduces pollutant Oxidation effectiveness；Present invention interval is aerated after 45 minutes, will not make Fe²⁺It is converted into Fe³⁺, Fe caused by iron-carbon micro-electrolysis²⁺It can carry High Fenton's reaction speed, strengthen pollutant oxidation effectiveness.Sediment after the reaction of iron carbon, Fenton's reaction and aeration, in sewage Impurity and sediment are all sunk in sludge hopper；

In addition, the iron cement slag that one layer of micro-electrolysis reaction layer above is split away off, may be attached to micro-electrolysis reaction layer Surface, therefore the intermittent aerating in light electrolysis unit, to be desorbed the iron cement slag of micro-electrolysis reaction layer surface, improve light electrolysis-sweet smell The reaction effect of device.

F. the aerator continuous aeration of oxidizing, flocculating unit bottom, gas-water ratio 6~15：1；Carrying in light electrolysis unit Fe²⁺Sewage flowed into by the outlet pipe on effluent trough in the center water inlet pipe of oxidizing, flocculating unit, intake bottom of the tube by center Umbrella shape diffuser enter oxidizing, flocculating unit bottom；By the aerator entrance of oxidizing, flocculating unit bottom, continuous aeration, Gas-water ratio 6~15：1, by Fe in waste water²⁺It is oxidized to rear Fe³⁺, remove the colourity of sewage；

G. when waste water level is reached in effluent trough, the pH on-line computing models in effluent trough, the pH value of waste water is monitored, when pH is small NaOH sensing dosing pumps are automatically turned on when 6, NaOH solution are added in the water inlet pipe of center, generation floccule Fe (OH)₃, enter One step sweeps along pollutant to be deposited in sludge hopper；

Water outlet after light electrolysis-Fenton's reaction enters oxidizing, flocculating unit, adds NaOH and is continuously oxygenated, can play with Lower effect：The Fe that will be remained in waste water²⁺It is oxidized to Fe³⁺, slough Fe²⁺Colourity, water outlet is avoided to return color phenomenon；Make organic in waste water The further oxidation Decomposition of thing；Floccule body is formed under alkalescence condition, aeration plays stirring action.

H. waste water is flowed into the center of precipitation unit by the outlet pipe of effluent trough bottom right side after oxidizing, flocculating cell processing In water inlet pipe, precipitation unit bottom is entered, is further precipitated, swash plate stops that the sediment in waste water further sinks Form sediment, be deposited in sludge hopper, the waste water level after processing gradually rises enters subsequent processing by the outlet pipe in precipitation unit Reason；

I. when being full of sediment in the sludge hopper of any cell in light electrolysis unit, oxidizing, flocculating unit and precipitation unit When, discharge pipeline corresponding to opening carries out spoil disposal；

J. when the module type filler in light electrolysis unit has been used, or stoppage in transit is safeguarded, wastewater influent pump and H are closed₂O₂Add Waste water in light electrolysis unit is all sent into oxidation wadding by Teat pipette, the suction pump opened on the outlet pipe of light electrolysis unit Coagulate in unit, the valve closed on the outlet pipe connected with this light electrolysis unit, open what is connected with another light electrolysis unit Valve, wastewater influent pump and H on outlet pipe₂O₂Dosing pump, it is ensured that sewage disposal is continuously uninterruptedly carried out.

K. remove and close wastewater influent pump and H₂O₂Effluent trough in the light electrolysis unit of dosing pump, by light electrolysis unit Interior micro-electrolysis reaction layer is taken out successively, then is sequentially placed into new micro-electrolysis reaction layer, and effluent trough is positioned over into light electrolysis unit On, in case the light electrolysis unit that is used next time stop transport safeguard or module type filler using it is complete when enable.

Preferably, the micro-electrolysis reaction layer is made up of supporting plate and module type filler, and mould is set side by side with supporting plate Group formula filler, described module type filler are made up of laminal filter, PVC brackets, and described PVC brackets are cuboid-type, built-in Neck, described laminal filter are inserted vertically into neck；

The mass fraction of each component and mesh number are respectively in described laminal filter：

Cast iron or pig scrap：55~60 parts, 50~60 mesh；

Coke blacking：30~35 parts, 60~70 mesh；

Copper powder：5~10 parts, 50~60 mesh；

Binding agent：3~5 parts；

Binding agent includes fine sand and portland cement, mass ratio 1:2~3；

Its making step is as follows：

Wire netting using size as 8*8*0.8, it is skeleton, after high pressure is compressing, enters stove nitrogen charging high-temperature calcination shaping, Temperature is：1050~1200 DEG C, the firing time is：4~5 hours.

Due to adding copper, form the potential difference bigger than conventional iron carbon filler, have use when be not passivated, not fragmentation, The feature such as do not lump；Laminal filter element number in module type filler, visual waste water quality situation are flexibly held, suitably increased Subtract；Described fagging is made up of fiberglass grizzly bar, and load-bearing is big.

The conventional iron carbon filler profile used is generally spheroidal, granular, annular or strip, is typically pressed into by physics Type, do not solidify by high-temperature firing, in use easily softening, Song Hua, be compacted, filler surface shape easy to fall off after longtime running Into passivating film, the suspended particulate such as part iron carbon mud is gradually deposited at the filler surface in bottom, has obstructed filler and waste water Effectively contact, causes water treatment effect to reduce；The present invention uses this form being separated in layers, and avoids suspended particulate deposition Filler surface, iron carbon filler is effectively fully contacted with waste water, improve water treatment effect；

In traditional iron-carbon micro-electrolysis reactor, filler typically uses landfill state, and stack up is not relatively solid during use Fixed structural support, filler size diminishes after long-term operating, and porosity declines between filler；Iron content more heavier mass in upper strata is filled out Material gradually sinks, and causes filler distribution in pond uneven while crushing lower floor's smaller filler, forms cutout or slough, not only Waste water fluidised form is influenceed, light electrolysis effect is influenceed and causes treatment effeciency to decline, also greatly increase follow-up replacement difficulty；Even if Whole waste water are cleared up in emptying reactor, if open-assembly time is longer, it is also possible to whole packing layer is all lumpd, caused Reactor is entirely scrapped；The present invention sets multilayer micro-electrolysis reaction layer in light electrolysis unit, is separated in layers, each layer is by branch Fagging supports, and is set side by side with multigroup module type filler in supporting plate, described module type filler is by laminal filter, PVC brackets Composition, described PVC brackets are cuboid-type, built-in neck, and described laminal filter is inserted vertically into neck, longtime running, Sink in the absence of filler, cause skewness, and form the phenomenon of cutout or slough, caking is also not present or makes reactor report Useless situation, light electrolysis stabilised efficiency is efficient, after running a period of time, can take out micro-electrolysis reaction layer, PVC bracket energy Enough recovery, are continuing with after re-replacing filler, convenient operation, save cost, improve filler utilization rate, improve sewage disposal effect Fruit；

In conventional iron-carbon micro-electrolysis-Fenton's reaction device, micro-electrolysis stuffing is stacked upon as one layer, due to support Plate limited load bearing capacities, packing layer thickness is typically small, and waste water, can not during continuing up plug-flow after light electrolysis layer It is in contact again with iron carbon filler, light electrolysis effect is limited；The present invention sets multilayer micro-electrolysis reaction in light electrolysis unit Layer, is separated in layers, each layer is supported by supporting plate, and multigroup module type filler is set side by side with supporting plate, and waste water pushes up Stream can contact with multilayer micro-electrolysis reaction layer, add the time of contact of waste water and filler, treatment effeciency is than traditional light electrolysis Filler is more excellent, and treatment effect is stable.

It is large-scale that the multistage light electrolysis-Fenton of the present invention reflects that device available for small-sized sewage treating system can also be used for city Sewage disposal system, the physical dimension of the technical characteristic of different parameters need to be only designed according to different application scenarios.

3. beneficial effect

Compared to prior art, beneficial effects of the present invention are：

(1) present invention is directed to the floccule body formed after Fenton's reaction, and because aeration time is longer, flco surface attachment has very More micro-bubbles are not easy to precipitate, the ineffective phenomenon of conventional precipitation method；Swash plate is set to strengthen sedimentation effect；Aeration dress The hole put is used to be aerated, and the hole of water-distributing device is used for water distribution, to prevent that flco or particulate matter block aperture in waste water；These are set Described device can be made effectively to run, reduce Breakdown Maintenance rate, ensure that device normal work；The light electrolysis- Fenton's reaction device appearance is in square, and inside is equally divided into 4 units along opposite side midpoint；Two light electrolysis units are in parallel, normal fortune One only being used during row, stoppage in transit opens another unit when safeguarding, it can be ensured that device is continuously run, when being not in replacing filler, Or reactor when safeguarding of stopping transport wants the situation of Temporarily Closed to occur；

(2) sewage of the present invention enters sewage water inlet pipe, H through wastewater influent pump₂O₂H in storage tank₂O₂Solution is through H₂O₂Dosing Pump, by H₂O₂Chemical feed pipe is from H₂O₂Chemical feed pipe cutting face is flowed out, and into sewage water inlet pipe, is collaborated with sewage, both mix in pipeline It is sufficiently mixed at device；The sewage for flowing out pipe-line mixer enters in the water-distributing device in light electrolysis unit, flows on water-distributing device Main, flowed out out of hole on branch pipe, as sewage is constantly flowed into light electrolysis unit, water level rise, sewage gradually with Each micro-electrolysis reaction layer contact, sewage and laminal filter, i.e. iron carbon filler fully contact, and in acid condition, iron carbon occur Micro-electrolysis reaction, galvanic effect is formed between iron and carbon in waste water, difference in Electrode Potential 1.2V, is containing acidic electrolyte bath Electrochemical reaction occurs in the aqueous solution, nascent state atom [H] and Fe caused by reaction²⁺Etc. can with waste water many components occur Redox reaction, can reach makes waste water COD reduction, BOD rises, biodegradability (B/C) raising and waste water decoloring and other effects；

(3) H that the present invention adds₂O₂With iron-carbon micro-electrolysis reaction caused by Fe²⁺Mix, be less than 4 acid in pH Property under the conditions of, Fenton's reaction occurs, obtains the very strong OH of oxidability (oxidizing electrode current potential 2.80V), so as to by waste water Pollutant oxidation Decomposition reaction, have the advantages that to be swift in response, aoxidize more thoroughly, do not produce secondary pollution；

(4) iron-carbon micro-electrolysis reaction of the present invention and Fenton's reaction are all to be reacted in acid condition, iron-carbon micro-electrolysis During caused Fe²⁺It is one of major pharmaceutical agent of Fenton's reaction, iron-carbon micro-electrolysis and Fenton oxidation technology is combined together, Form a kind of new wastewater treatment high-level oxidation technology --- light electrolysis-Fenton oxidation technology, in acid condition, the micro- electricity of iron carbon Fe caused by solution reaction²⁺, with adding the H in waste water₂O₂Generation Strong oxdiative reacts, and has reduced Fenton's reaction Fe²⁺Dosage, improve Disposal ability of the device to pollutant；Conventional reactor, does not have oxygenic aeration after Fenton oxidation terminates, causes in water outlet Fe²⁺It is more, add the Fe (OH) formed after alkali₂Lighter weight is not easy to precipitate, and due to the Fe of residual in waste water²⁺Colour developing causes waste water Colourity is higher, and visual sensory is poor；The present invention was not both aerated directly, also without alkali is added, avoided the hair of above-mentioned two situations It is raw；

(5) in conventional light electrolysis-Fenton's reaction device, H is added in light electrolysis unit mostly₂O₂After proceed by exposure Gas, a large amount of oxygenations can make Fe²⁺It is converted into Fe³⁺, and Fe²⁺It is one of major pharmaceutical agent of Fenton's reaction, thus slows down Fenton's reaction Speed, reduce pollutant oxidation effectiveness；Present invention interval is aerated after 45 minutes, will not make Fe²⁺It is converted into Fe³⁺, iron-carbon micro-electrolysis Caused Fe²⁺Fenton's reaction speed can be improved, strengthens pollutant oxidation effectiveness.After the reaction of iron carbon, Fenton's reaction and aeration Sediment, impurity and sediment in sewage are all sunk in sludge hopper；In addition, one layer of micro-electrolysis reaction layer above is split away off Iron cement slag, the surface of micro-electrolysis reaction layer, therefore the intermittent aerating in light electrolysis unit may be attached to, to be desorbed micro- electricity The iron cement slag of solution reaction layer surface, improve the reaction effect of light electrolysis-Fenton device；

(6) water outlet after light electrolysis-Fenton's reaction of the present invention enters oxidizing, flocculating unit, adds NaOH and is continuously oxygenated, Following effect can be played：The Fe that will be remained in waste water²⁺It is oxidized to Fe³⁺, slough Fe²⁺Colourity, water outlet is avoided to return color phenomenon；Make The further oxidation Decomposition of useless Organic substance in water；Floccule body is formed under alkalescence condition, aeration plays stirring action；

(7) laminal filter of the present invention is after copper powder, binding agent molding slabbing are added in conventional iron carbon filler It is molded through high-temperature firing；Due to adding copper, the potential difference bigger than conventional iron carbon filler is formed, has and is not passivated, no when using Fragmentation, the feature such as do not lump；Laminal filter element number in module type filler, visual waste water quality situation are flexibly held, and are carried out Appropriate increase and decrease；Described fagging is made up of fiberglass grizzly bar, and load-bearing is big；

(8) the conventional iron carbon filler profile used is generally spheroidal, granular, annular or strip, typically by physics pressure Synthesis type, do not solidify by high-temperature firing, in use easily softening, Song Hua, be compacted, filler surface is easily de- after longtime running Fall to form passivating film, the suspended particulate such as part iron carbon mud is gradually deposited at the filler surface in bottom, has obstructed filler with giving up Effective contact of water, causes water treatment effect to reduce；The present invention uses this form being separated in layers, and avoids suspended particulate Deposit filler surface, iron carbon filler is effectively fully contacted with waste water, improve water treatment effect；

(9) in traditional iron-carbon micro-electrolysis reactor, filler typically uses landfill state, and stack up is not relative during use Fixed structural support, filler size diminishes after long-term operating, and porosity declines between filler；The more heavier mass of upper strata iron content Filler gradually sinks, and causes filler distribution in pond uneven while crushing lower floor's smaller filler, forms cutout or slough, no Waste water fluidised form is only influenceed, light electrolysis effect is influenceed and causes treatment effeciency to decline, also greatly increase follow-up replacement difficulty；I.e. Cleared up whole waste water in emptying reactor, if open-assembly time is longer, it is also possible to whole packing layer is all lumpd, lead Reactor is caused entirely to scrap；The present invention in light electrolysis unit set multilayer micro-electrolysis reaction layer, be separated in layers, each layer by Supporting plate is supported, and multigroup module type filler is set side by side with supporting plate, and described module type filler is held in the palm by laminal filter, PVC Frame forms, and described PVC brackets are cuboid-type, and built-in neck, described laminal filter is inserted vertically into neck, long-term to transport OK, sink in the absence of filler, cause skewness, and form the phenomenon of cutout or slough, caking is also not present or makes reaction The situation that device is scrapped, light electrolysis stabilised efficiency is efficient, after running a period of time, can take out micro-electrolysis reaction layer, PVC supports Frame can reclaim, and be continuing with after re-replacing filler, convenient operation, save cost, improve filler utilization rate, improve at sewage Manage effect；

(10) in conventional iron-carbon micro-electrolysis-Fenton's reaction device, micro-electrolysis stuffing is stacked upon as one layer, due to Supporting plate limited load bearing capacities, packing layer thickness is typically small, and waste water is after light electrolysis layer, during continuing up plug-flow It can not be in contact again with iron carbon filler, light electrolysis effect is limited；The present invention sets multilayer light electrolysis in light electrolysis unit Conversion zone, be separated in layers, each layer supports by supporting plate, is set side by side with multigroup module type filler in supporting plate, waste water to Upper plug-flow can contact with multilayer micro-electrolysis reaction layer, add the time of contact of waste water and filler, and treatment effeciency is more micro- than tradition Electrolysis filler is more excellent, and treatment effect is stable；

(11) multistage light electrolysis of the invention-Fenton reflection device can also be used for city available for small-sized sewage treating system Down-stream processing system, the physical dimension for the technical characteristic that only need to design different parameters according to different application scenarios are Can.

Brief description of the drawings

Fig. 1 is the water-distributing device schematic diagram of the present invention；

Fig. 2 is the branch pipe cross-sectional view of the present invention；

Fig. 3 is the H of the present invention₂O₂The structural representation of throwing device；

Fig. 4 is module type iron carbon filler schematic diagram of the present invention.

1st, wastewater influent pump；2、H₂O₂Dosing pump；2-1、H₂O₂Storage tank；2-2、H₂O₂Chemical feed pipe；3rd, pipe-line mixer；4- 14-1 mains；4-14-2, branch pipe；4-15 module type fillers；4-15-1, laminal filter；4-15-2, PVC bracket.

Embodiment

The present invention is further described below with reference to specific embodiment.

Embodiment 1

With reference to Fig. 1-4, a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler, including wastewater influent pump 1、H₂O₂Throwing device and pipe-line mixer 3, it also includes light electrolysis-Fenton's reaction device, wherein, the wastewater influent pump 1 is set Put on sewage water inlet pipe, sewage water inlet pipe and the H₂O₂After throwing device connection, H₂O₂Throwing device mixes with the pipeline Clutch 3 is connected, and described pipe-line mixer 3 is connected by pipeline with the light electrolysis-Fenton's reaction device；

The H₂O₂Throwing device includes H₂O₂Storage tank 2-1, H₂O₂Chemical feed pipe 2-2 and H₂O₂Dosing pump 2；Described H₂O₂Storage Groove 2-1 bottom and H₂O₂Chemical feed pipe 2-2 is connected, described H₂O₂Chemical feed pipe 2-2 is provided with H₂O₂Dosing pump 2.

The H₂O₂Vertical lines of the chemical feed pipe 2-2 along sewage water inlet pipe is inserted into the center position of cross section, H₂O₂Chemical feed pipe Outlets of the 2-2 in sewage water inlet pipe, to be cut along water (flow) direction reverse side, cutting face and water (flow) direction be at 45 °~60 ° of angles, expand Big H₂O₂Chemical feed pipe 2-2 discharge area, H₂O₂Opening position that chemical feed pipe 2-2 connects with sewage water inlet pipe and pipe-line mixer 3 it Between distance be more than 300mm so that H₂O₂It can be well mixed with sewage.

The bottom of the light electrolysis unit is provided with discharge pipeline, and discharge pipeline is connected with sludge hopper, and aeration is provided with sludge hopper Device, aerator top are provided with water-distributing device, 3-6 layer micro-electrolysis reaction layers are provided with above water-distributing device, useless to increase The time of contact of water and filler, it is ensured that micro-electrolysis reaction effect, micro-electrolysis reaction layer top are provided with effluent trough, and effluent trough is right Side bottom is provided with outlet pipe, and plane where plane where plane, water-distributing device where aerator and micro-electrolysis reaction layer is mutual Parallel, described water-distributing device is connected by pipeline with described pipe-line mixer 3, the outlet pipe in the light electrolysis unit Connected with the center water inlet pipe in oxidizing, flocculating unit.Intake by light electrolysis unit bottom, the effluent trough on light electrolysis unit top Water outlet, body refuse caused by operation discharge from the discharge pipeline for being arranged on light electrolysis unit bottom.

The micro-electrolysis reaction layer is made up of supporting plate and module type filler 4-15, and module type is set side by side with supporting plate Filler 4-15, described module type filler 4-15 are made up of laminal filter 4-15-1, PVC bracket 4-15-2, described PVC brackets 4-15-2 is cuboid-type, built-in neck, and described laminal filter 4-15-1 is inserted vertically into neck, every layer of micro-electrolysis reaction layer On share 600~1800 laminal filter 4-15-1.

NaOH automatic medicament feeding systems are provided with above the oxidizing, flocculating unit, NaOH automatic medicament feeding systems are stored up by NaOH solution Groove, NaOH chemical feed pipes and NaOH sensing dosing pump compositions, the bottom of described NaOH solution storage tank connect with NaOH chemical feed pipes, institute The NaOH chemical feed pipes stated are provided with NaOH sensing dosing pumps, and described NaOH chemical feed pipes are stretched into the water inlet pipe of center, center water inlet Pipe is arranged on the central axis of oxidizing, flocculating unit, going out at the top of the Upper vertical insertion oxidizing, flocculating unit of center water inlet pipe PH on-line computing models are provided with tank, in effluent trough, described pH on-line computing models are connected with NaOH sensing dosing pumps, water outlet Groove bottom right side is provided with outlet pipe, and center water inlet bottom of the tube is provided with umbrella shape diffuser, and the bottom of oxidizing, flocculating unit is provided with Aerator, sludge hopper is provided with below aerator, discharge pipeline, the oxidizing, flocculating unit are provided with below sludge hopper Interior outlet pipe connects with the center water inlet pipe in precipitation unit.

Described aerator is identical with water-distributing device structure, is made up of main 4-14-1, branch pipe 4-14-2, branch pipe 4- 14-2 is symmetrically and evenly arranged on main 4-14-1 both sides, and branch pipe 4-14-2 is vertical with main 4-14-1, branch pipe 4-14-2 tables Hole is provided with face, vertical line both sides are evenly distributed in 45 ° of angles with branch pipe 4-14-2 cross sections vertical direction.To prevent waste water Middle flco or particulate matter block aperture, and the main 4-14-1 of described aerator and the air compressor machine of peripheral hardware connect, air compressor machine to Compressed air is passed through in main 4-14-1, the hole of aerator is used to be aerated, can be by Fe²⁺(blue-green) is oxidized to Fe³⁺It is (pale brown Color), it is more beneficial for precipitating and can further reduces effluent color dilution, the tiny particles content on micro-electrolysis stuffing surface is attached to stripping And body refuse, particulate matter, which adheres to, when avoiding using for a long time causes light electrolysis effect to decline, and water-distributing device is used for water distribution.

The central axis of the precipitation unit is provided with center water inlet pipe, center water inlet pipe Upper vertical insertion precipitation unit In the effluent trough at top, the side bottom of effluent trough is connected provided with outlet pipe, and center water inlet pipe is passed through and is arranged in precipitation unit Swash plate, for the floccule body formed after Fenton's reaction, because aeration time is longer, flco surface attachment has many micro-bubbles It is not easy to precipitate, the ineffective phenomenon of conventional precipitation method；Swash plate is strengthening sedimentation effect；Center water inlet bottom of the tube is provided with Umbrella shape diffuser, precipitation unit bottom are provided with sludge hopper, discharge pipeline are provided with below sludge hopper.

The center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, and bottom lengths are (1.2~1.5) D, the sludge hopper front view are shaped as upside-down trapezoid, and the spoil disposal pipe diameter is not less than 200mm, to prevent mud Slag, which blocks, causes spoil disposal not smooth.

A builds a kind of multistage light electrolysis-Fenton's reaction device of described module type iron carbon filler according to described above；

B. discharge pipeline is reviewed and validate to be closed；

C. valve, wastewater influent pump 1 and the H closed on an outlet pipe connected with light electrolysis unit₂O₂Dosing pump 2, makes Light electrolysis unit in light electrolysis-Fenton's reaction device only has one and can be used in sewage disposal；

D. valve, wastewater influent pump 1 and the H on the outlet pipe that another is connected with light electrolysis unit are opened₂O₂Dosing pump 2, The light electrolysis unit in light electrolysis-Fenton's reaction device is only had one and can be used in sewage disposal；Open H₂O₂Dosing pump 2 to H is added in sewage₂O₂；Sewage enters sewage water inlet pipe, H through wastewater influent pump 1₂O₂H in storage tank 2-1₂O₂Solution is through H₂O₂Dosing Pump 2, by H₂O₂Chemical feed pipe 2-2 is from H₂O₂Chemical feed pipe 2-2 cutting faces are flowed out, and into sewage water inlet pipe, are collaborated with sewage, Liang Zhe It is sufficiently mixed at pipe-line mixer 3；

Light electrolysis operation principle is：

It is that negative electrode generation is micro- using iron as anode, carbon (copper) when waste water fully contacts with improvement iron-carbon micro-electrolysis filler unit Cell reaction, electrode reaction are as follows：

Anode (Fe):Fe-2e=Fe²⁺ E⁰=-0.44V,

Negative electrode (C)：2H⁺+ 2e=H₂ E⁰=0V,

Following reaction occurs for negative electrode in the presence of aerobic：

O₂+4H⁺+ 4e=H₂O E⁰=-1.23V

O₂+2H₂O+4e=5OH^-- E⁰=0.40V

Copper powder is as cathode material, electrode potential in acid condition：E⁰=-0.34V；Electrode under alkalescence condition Current potential：E⁰=-0.22V.The presence of copper powder expands the potential difference and applicable pH range of micro-electrolysis reaction, i.e., micro- in conventional iron carbon It can still make micro-electrolysis reaction continue to carry out under the bad pH partial neutrals of electrolysis effectiveness even alkalescence condition, make the pollutant in waste water Decomposed under light electrolysis effect more thorough.

The operation principle of Fenton's reaction is：

Hydrogen peroxide (H is added in micro-electrolysis reactor₂O₂) when, Fe caused by micro-electrolysis reaction²⁺It is catalyzed H₂O₂Decompose and produce OH with strong oxidizing property：

Fe²⁺+H₂O₂=Fe³⁺+OH^-+·OH E⁰=2.80V

OH has very strong oxidisability, and especially oxidability is very strong in acid waste water, and F is only second in nature.Often The small organic molecule seen can complete oxidation, the dysoxidizable fragrant type organic matter of common oxidizer and some heterocyclics can also be had The almost all such as machine thing decompose.

The sewage for flowing out pipe-line mixer 3 enters in the water-distributing device in light electrolysis unit, flows into dry on water-distributing device Pipe 4-14-1, flowed out out of hole on branch pipe 4-14-2, as sewage is constantly flowed into light electrolysis unit, water level rises, dirty Water gradually contacts with each micro-electrolysis reaction layer, and sewage and laminal filter 4-15-1, i.e. iron carbon filler fully contacts, in acid bar Under part, iron-carbon micro-electrolysis reaction occurs, forms galvanic effect in waste water between iron and carbon, difference in Electrode Potential 1.2V, containing Have and electrochemical reaction occurs in the aqueous solution of acidic electrolyte bath, nascent state atom [H] and Fe caused by reaction²⁺Etc. can with waste water Many components redox reaction occurs, can reach reduce waste water COD, BOD rises, biodegradability (B/C) improve and useless Water decolorization and other effects；

Also some do not have oxygenic aeration after Fenton oxidation terminates, and cause Fe in water outlet²⁺It is more, add the Fe formed after alkali (OH)₂Lighter weight is not easy to precipitate, and due to the Fe of residual in waste water²⁺Colour developing causes chroma in waste water higher, and visual sensory is poor； The present invention was not both aerated directly, also without alkali is added, avoided the generation of above-mentioned two situations.

Micro-electrolysis reaction layer is made up of supporting plate and module type filler 4-15, and module type filler is set side by side with supporting plate 4-15, described module type filler 4-15 are made up of laminal filter 4-15-1, PVC bracket 4-15-2, described PVC brackets 4- 15-2 is cuboid-type, built-in neck, and described laminal filter 4-15-1 is inserted vertically into neck；

The mass fraction of each component and mesh number are respectively in laminal filter 4-15-1：

Cast iron or pig scrap：55~60 parts, 50~60 mesh；

Coke blacking：30~35 parts, 60~70 mesh；

Copper powder：5~10 parts, 50~60 mesh；

Binding agent：3~5 parts；

Binding agent includes fine sand and portland cement, mass ratio 1:2~3；

Its making step is as follows：

Wire netting using size as 8*8*0.8 is skeleton, after high pressure is compressing, enters stove nitrogen charging high-temperature calcination shaping, Temperature is：1050~1200 DEG C, the firing time is：4~5 hours.Finished product laminal filter 4-15-1 apparent sizes are：140mm (length) × 140mm (width) × 8mm (thickness).

Due to the addition of copper；Form the potential difference bigger than conventional iron carbon filler, have be not passivated when using, not fragmentation, The feature such as do not lump；Laminal filter element number in module type filler 4-15, visual waste water quality situation are flexibly held, fitted Work as increase and decrease；Described fagging is made up of fiberglass grizzly bar, and load-bearing is big.

In traditional iron-carbon micro-electrolysis reactor, filler typically uses landfill state, and stack up is not relatively solid during use Fixed structural support, filler size diminishes after long-term operating, and porosity declines between filler；Iron content more heavier mass in upper strata is filled out Material gradually sinks, and causes filler distribution in pond uneven while crushing lower floor's smaller filler, forms cutout or slough, not only Waste water fluidised form is influenceed, light electrolysis effect is influenceed and causes treatment effeciency to decline, also greatly increase follow-up replacement difficulty；Even if Whole waste water are cleared up in emptying reactor, if open-assembly time is longer, it is also possible to whole packing layer is all lumpd, caused Reactor is entirely scrapped；The present invention sets multilayer micro-electrolysis reaction layer in light electrolysis unit, is separated in layers, each layer is by branch Fagging supports, and is set side by side with multigroup module type filler 4-15 in supporting plate, described module type filler 4-15 is by laminal filter 4-15-1, PVC bracket 4-15-2 are formed, and described PVC brackets 4-15-2 is cuboid-type, built-in neck, and described sheet is filled out Material 4-15-1 is inserted vertically into neck, longtime running, is sunk in the absence of filler, causes skewness, and forms cutout or stagnant water The phenomenon in area, caking or the situation for scrapping reactor being also not present, light electrolysis stabilised efficiency is efficient, after running a period of time, Micro-electrolysis reaction layer can be taken out, PVC brackets 4-15-2 can be reclaimed, and be continuing with after re-replacing filler, convenient behaviour Make, save cost, improve filler utilization rate, improve wastewater treatment efficiency；

PVC brackets 4-15-2 appearance and size is：150mm (length) × 150mm (width) × 150mm (height), the inside is reserved to insert Groove, it at most can be inserted into 6 laminal filter 4-15-1；Certain space is left between laminal filter 4-15-1, is advantageous to waste water and leads to The iron cement formed is crossed and reacts to fall into bottom of pond sludge hopper.

In conventional iron-carbon micro-electrolysis-Fenton's reaction device, micro-electrolysis stuffing is stacked upon as one layer, due to support Plate limited load bearing capacities, packing layer thickness is typically small, and waste water, can not during continuing up plug-flow after light electrolysis layer It is in contact again with iron carbon filler, light electrolysis effect is limited；The present invention sets multilayer micro-electrolysis reaction in light electrolysis unit Layer, is separated in layers, and each layer supports by supporting plate, is set side by side with multigroup module type filler 4-15 in supporting plate, waste water to Upper plug-flow can contact with multilayer micro-electrolysis reaction layer, add the time of contact of waste water and filler, and treatment effeciency is more micro- than tradition Electrolysis filler is more excellent, and treatment effect is stable.

NaOH is added in water outlet after light electrolysis-Fenton's reaction and is continuously oxygenated, following effect can be played：By in waste water The Fe of residual²⁺It is oxidized to Fe³⁺, slough Fe²⁺Colourity, water outlet is avoided to return color phenomenon；Make the further oxidation point of useless Organic substance in water Solution；Floccule body is formed under alkalescence condition, aeration plays stirring action.

J. when the module type filler in light electrolysis unit has been used, or stoppage in transit is safeguarded, wastewater influent pump 1 and H are closed₂O₂ Waste water in light electrolysis unit is all sent into oxygen by dosing pump 2, the suction pump opened on the outlet pipe of light electrolysis unit Change in flocculation unit, the valve closed on the outlet pipe connected with this light electrolysis unit, open and connect with another light electrolysis unit Valve, wastewater influent pump and H on logical outlet pipe₂O₂Dosing pump, it is ensured that sewage disposal is continuously uninterruptedly carried out.

K. remove and close wastewater influent pump 1 and H₂O₂Effluent trough in the light electrolysis unit of dosing pump 2, by light electrolysis list Light electrolysis layer in member is taken out successively, then is sequentially placed into new light electrolysis layer, and effluent trough is positioned on light electrolysis unit, in case The light electrolysis unit that is used next time stop transport safeguard or module type filler 4-15 using it is complete when enable.

Embodiment 2

Certain printing and dyeing mill's high concentration production waste water, the waste water yield is about 300t/d；PH3.3~4.6, average 3.9； COD5000~9200mg/L, average 7300mg/L；B/C<0.15, wastewater biodegradability is poor.It is proposed that a kind of module type iron carbon is filled out Multistage light electrolysis-Fenton's reaction device of material, as Figure 1-4, its structure and application method with embodiment 1, wherein, H₂O₂Add The distance between opening position that pencil 2-2 connects with sewage water inlet pipe and pipe-line mixer 3 are 301mm, micro-electrolysis reaction layer Quantity is 3 layers, a diameter of 201mm of discharge pipeline, adds H₂O₂After end, the aerator of light electrolysis unit exposed at interval of 45 minutes Gas 10 minutes, is set side by side with 200 groups of module type filler 4-15 in supporting plate, the laminal filter in each layer of micro-electrolysis reaction layer 4-15-1 quantity is 600.

H₂O₂Outlets of the chemical feed pipe 2-2 in sewage water inlet pipe, cut along water (flow) direction reverse side, cutting face and water (flow) direction Angle at 45 °；Center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, bottom lengths 1.2D； The mass fraction of each component and mesh number are respectively in laminal filter 4-15-1：

Cast iron or pig scrap：55 parts, 50 mesh；

Coke blacking：30 parts, 60 mesh；

Copper powder：5 parts, 50 mesh；

Binding agent：3 parts；

Binding agent includes fine sand and portland cement, mass ratio 1:2；After high pressure is compressing, enter stove nitrogen charging height Temperature calcining shaping, temperature are：1050 DEG C, the firing time is：4 hours.

Branch pipe 4-14-2 quantity is 8 pairs totally 16, shares two holes to partner on every branch pipe 4-14-2, totally 7 It is right.

Waste water is pumped into device from bottom, and it is 60min to control hydraulic detention time, and hydrogen peroxide dosage is 4.0mL/L, often 45 minutes 10 clocks of aeration in interval, gas-water ratio 6：1；Continuous aeration in oxidizing, flocculating reactor, gas-water ratio 6：1, handle water outlet Water quality is：PH is 6.7, COD 3160mg/L, and COD clearances are 56.7%, B/C=0.36, and wastewater biodegradability obtains larger Improve, improvement iron carbon filler does not occur blocking, crushed and hardened phenomenon in reactor during use, integrated apparatus operation shape Condition is good.

Embodiment 3

Jiangsu factory high concentration agricultural chemical production waste water, the waste water yield is about 90t/d；PH1.8~3.2, average 2.6；COD4200~6500mg/L, average 5100mg/L；B/C<0.15, wastewater biodegradability is poor, proposes a kind of module type iron Multistage light electrolysis-Fenton's reaction device of carbon filler, as Figure 1-4, its structure and application method with embodiment 1, wherein, H₂O₂The distance between opening position that chemical feed pipe 2-2 connects with sewage water inlet pipe and pipe-line mixer 3 are 500mm, micro-electrolysis reaction The quantity of layer is 6 layers, a diameter of 300mm of discharge pipeline, adds H₂O₂After end, the aerator of light electrolysis unit is at interval of 45 points Clock is aerated 15 minutes, is set side by side with 150 groups of module type filler 4-15 in supporting plate, the sheet in each layer of micro-electrolysis reaction layer Filler 4-15-1 quantity is 900.

H₂O₂Outlets of the chemical feed pipe 2-2 in sewage water inlet pipe, cut along water (flow) direction reverse side, cutting face and water (flow) direction Into 60 ° of angles；Center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, bottom lengths 1.5D； The mass fraction of each component and mesh number are respectively in laminal filter 4-15-1：

Cast iron or pig scrap：60 parts, 60 mesh；

Coke blacking：35 parts, 70 mesh；

Copper powder：10 parts, 60 mesh；

Binding agent：5 parts；

Binding agent includes fine sand and portland cement, mass ratio 1:3；After high pressure is compressing, enter stove nitrogen charging height Temperature calcining shaping, temperature are：1200 DEG C, the firing time is：5 hours.

Branch pipe 4-14-2 quantity is 10 pairs totally 20, shares two holes to partner on every branch pipe 4-14-2, totally 9 It is right.

Waste water is pumped into device from bottom, and it is 120min to control hydraulic detention time, and hydrogen peroxide dosage is 3.0mL/L, It was aerated 15 minutes at interval of 45 minutes, gas-water ratio 10：1；Continuous aeration in oxidizing, flocculating reactor, gas-water ratio 12：1, place Managing effluent quality is：PH is 6.4, COD 1780mg/L, and COD clearances are 65.10%, B/C=0.39, wastewater biodegradability It is greatly improved.Improvement iron carbon filler does not occur blocking, crushed and hardened phenomenon in reactor during use, one makeup It is good to put operation conditions.

Embodiment 4

Zhejiang high concentration coking, the waste water yield is about 420t/d, measures waste water quality in regulating reservoir and is about： PH4.5, colourity 1200, COD5860mg/L, B/C<0.15.It is proposed that a kind of multistage light electrolysis-Fenton of module type iron carbon filler is anti- Answer device, as Figure 1-4, its structure and application method with embodiment 1, wherein, H₂O₂Chemical feed pipe 2-2 connects with sewage water inlet pipe The distance between logical opening position and pipe-line mixer 3 are 800mm, and the quantity of micro-electrolysis reaction layer is 5 layers, and discharge pipeline is a diameter of 500mm, add H₂O₂After end, the aerator of light electrolysis unit was aerated 13 minutes at interval of 45 minutes, was set side by side in supporting plate It is equipped with 180 groups of module type filler 4-15, the quantity of the laminal filter 4-15-1 in each layer of micro-electrolysis reaction layer is 1800.

H₂O₂Outlets of the chemical feed pipe 2-2 in sewage water inlet pipe, cut along water (flow) direction reverse side, cutting face and water (flow) direction Into 50 ° of angles；Center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, bottom lengths 1.4D； The mass fraction of each component and mesh number are respectively in laminal filter 4-15-1：

Cast iron or pig scrap：58 parts, 55 mesh；

Coke blacking：34 parts, 67 mesh；

Copper powder：7 parts, 56 mesh；

Binding agent：4 parts；

Binding agent includes fine sand and portland cement, mass ratio 1:2.8；After high pressure is compressing, enter stove nitrogen charging High-temperature calcination is molded, and temperature is：1100 DEG C, the firing time is：4.5 hour.

Branch pipe 4-14-2 quantity is 9 pairs totally 18, shares two holes to partner on every branch pipe 4-14-2, totally 8 It is right.

It is 90min to control hydraulic detention time, and hydrogen peroxide dosage is 6.0mL/L, is aerated 15 minutes at interval of 45 minutes, Gas-water ratio is 15：1；Continuous aeration in oxidizing, flocculating reactor, gas-water ratio 15：1, handling effluent quality is：PH is 6.8, COD For 1840mg/L, COD clearances are 68.6%, B/C=0.37, and wastewater biodegradability is greatly improved.It is anti-during use Answer in device improvement iron carbon filler not occur blocking, crush and hardened phenomenon, integrated apparatus operation conditions are good.

Claims

1. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler, including wastewater influent pump (1), H₂O₂Add dress To put and pipe-line mixer (3), it is characterised in that it also includes light electrolysis-Fenton's reaction device, wherein, the wastewater influent pump (1) it is arranged on sewage water inlet pipe, sewage water inlet pipe and the H₂O₂After throwing device connection, H₂O₂Throwing device with it is described Pipe-line mixer (3) is connected, and described pipe-line mixer (3) is connected by pipeline with the light electrolysis-Fenton's reaction device；

The light electrolysis-Fenton's reaction device includes four units, wherein having two light electrolysis units, an oxidizing, flocculating unit With a precipitation unit, two light electrolysis units connect after being connected with oxidizing, flocculating unit, oxidizing, flocculating unit and precipitation unit Connection, described precipitation unit side are provided with outlet pipe, and described precipitation unit bottom is provided with discharge pipeline；The light electrolysis unit Bottom be provided with discharge pipeline；

Be provided with NaOH automatic medicament feeding systems above the oxidizing, flocculating unit, NaOH automatic medicament feeding systems by NaOH solution storage tank, NaOH chemical feed pipes and NaOH sensing dosing pump compositions, the bottom of described NaOH solution storage tank connects with NaOH chemical feed pipes, described NaOH chemical feed pipes be provided with NaOH sensing dosing pumps, described NaOH chemical feed pipes are stretched into the water inlet pipe of center, center water inlet pipe It is arranged on the central axis of oxidizing, flocculating unit, the water outlet at the top of the Upper vertical insertion oxidizing, flocculating unit of center water inlet pipe PH on-line computing models are provided with groove, in effluent trough, described pH on-line computing models are connected with NaOH sensing dosing pumps, effluent trough Bottom right side is provided with outlet pipe, and center water inlet bottom of the tube is provided with umbrella shape diffuser, and the bottom of oxidizing, flocculating unit, which is provided with, to expose Device of air, sludge hopper is provided with below aerator, is provided with discharge pipeline below sludge hopper, in the oxidizing, flocculating unit Outlet pipe connected with the center water inlet pipe in precipitation unit.

2. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 1, its feature exist In the H₂O₂Throwing device includes H₂O₂Storage tank (2-1), H₂O₂Chemical feed pipe (2-2) and H₂O₂Dosing pump (2)；Described H₂O₂Storage The bottom of groove (2-1) and H₂O₂Chemical feed pipe (2-2) connects, described H₂O₂Chemical feed pipe (2-2) is provided with H₂O₂Dosing pump (2).

3. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 2, its feature exist In the H₂O₂Vertical line of the chemical feed pipe (2-2) along sewage water inlet pipe is inserted into the center position of cross section, H₂O₂Chemical feed pipe (2- 2) outlet in sewage water inlet pipe, to be cut along water (flow) direction reverse side, cutting face and water (flow) direction be at 45 °~60 ° of angles, H₂O₂ The distance between opening position that chemical feed pipe (2-2) connects with sewage water inlet pipe and pipe-line mixer (3) are more than 300mm.

4. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 1, its feature exist In, the bottom of the light electrolysis unit is provided with discharge pipeline, and discharge pipeline is connected with sludge hopper, and aerator is provided with sludge hopper, Water-distributing device is provided with above aerator, is provided with 3-6 layer micro-electrolysis reaction layers above water-distributing device, on micro-electrolysis reaction layer Side is provided with effluent trough, and effluent trough bottom right side is provided with outlet pipe, plane where plane, water-distributing device where aerator with Plane where micro-electrolysis reaction layer is parallel to each other, and described water-distributing device is connected by pipeline with described pipe-line mixer (3), Described outlet pipe connects with the center water inlet pipe in oxidizing, flocculating unit.

5. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 1, its feature exist In the central axis of the precipitation unit is provided with center water inlet pipe, center water inlet pipe Upper vertical insertion precipitation unit top Effluent trough in, the side bottom of effluent trough connects with outlet pipe, and center water inlet pipe, which passes through, is arranged on swash plate in precipitation unit, Center water inlet bottom of the tube is provided with umbrella shape diffuser, and precipitation unit bottom is provided with sludge hopper, spoil disposal is provided with below sludge hopper Pipe；

The center water inlet pipe, a diameter of D, bottom set umbrella shape diffuser, 30 ° of diffuser corner, bottom lengths for (1.2~ 1.5) D, the sludge hopper front view are shaped as upside-down trapezoid, and the spoil disposal pipe diameter is not less than 200mm.

6. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 4, its feature exist In described aerator is identical with water-distributing device structure, is made up of main (4-14-1), branch pipe (4-14-2), branch pipe (4- Main (4-14-1) both sides 14-2) are symmetrically and evenly arranged on, branch pipe (4-14-2) is vertical with main (4-14-1), branch pipe Hole is provided with (4-14-2) surface, vertical line two is evenly distributed in 45 ° of angles with branch pipe (4-14-2) cross section vertical direction Side, the main (4-14-1) of described aerator are connected with the air compressor machine of peripheral hardware.

7. a kind of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 4, its feature exist In the micro-electrolysis reaction layer is made up of supporting plate and module type filler (4-15), and module type is set side by side with supporting plate and is filled out Expect (4-15), described module type filler (4-15) is made up of laminal filter (4-15-1), PVC brackets (4-15-2), described PVC brackets (4-15-2) are cuboid-type, built-in neck, and described laminal filter (4-15-1) is inserted vertically into neck, every layer 600~1800 laminal filters (4-15-1) are shared on micro-electrolysis reaction layer.

8. a kind of application method of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler, step are：

A. a kind of multistage light electrolysis-Fenton's reaction device of described module type iron carbon filler is built according to claim 1；

B. discharge pipeline is reviewed and validate to be closed；

C. valve, wastewater influent pump (1) and the H closed on an outlet pipe connected with light electrolysis unit₂O₂Dosing pump (2), makes Light electrolysis unit in light electrolysis-Fenton's reaction device only has one and can be used in sewage disposal；

D. valve, wastewater influent pump (1) and the H on the outlet pipe that another is connected with light electrolysis unit are opened₂O₂Dosing pump (2), The light electrolysis unit in light electrolysis-Fenton's reaction device is only had one and can be used in sewage disposal；Open H₂O₂Dosing pump (2) H is added into sewage₂O₂；

E. H is added₂O₂After end, the aerator of light electrolysis unit was aerated 10~15 minutes at interval of 45 minutes；

F. the aerator continuous aeration of oxidizing, flocculating unit bottom, gas-water ratio 6~15：1；Fe is carried in light electrolysis unit²⁺ Sewage flowed into by the outlet pipe on effluent trough in the center water inlet pipe of oxidizing, flocculating unit, by center intake bottom of the tube umbrella Shape diffuser enters the bottom of oxidizing, flocculating unit；By the aerator entrance of oxidizing, flocculating unit bottom, continuous aeration, air water Than 6~15：1, by Fe in waste water²⁺It is oxidized to rear Fe³⁺, remove the colourity of sewage；

G. when waste water level is reached in effluent trough, the pH on-line computing models in effluent trough, the pH value of waste water is monitored, when pH is less than 6 When automatically turn on NaOH sensing dosing pump, NaOH solution is added in the water inlet pipe of center, generation floccule Fe (OH)₃, enter one Step sweeps along pollutant to be deposited in sludge hopper；

H. waste water is flowed into the center water inlet of precipitation unit by the outlet pipe of effluent trough bottom right side after oxidizing, flocculating cell processing Guan Li, precipitation unit bottom is entered, is further precipitated, swash plate stops that the sediment in waste water further precipitates, and sinks Form sediment in sludge hopper, the waste water level after processing gradually rises is discharged by the outlet pipe in precipitation unit, at subsequent processing Reason；

I. when being full of sediment in the sludge hopper of any cell in light electrolysis unit, oxidizing, flocculating unit and precipitation unit, beat Discharge pipeline carries out spoil disposal corresponding to opening；

J. when the module type filler (4-15) in light electrolysis unit has used, or stop transport when safeguarding, close wastewater influent pump (1) and H₂O₂Dosing pump (2), the suction pump opened on the outlet pipe of light electrolysis unit all send the waste water in light electrolysis unit Enter in oxidizing, flocculating unit, the valve closed on the outlet pipe connected with this light electrolysis unit, open and another light electrolysis list Valve, wastewater influent pump (1) and H on the outlet pipe of member connection₂O₂Dosing pump (2), it is ensured that sewage disposal is continuously uninterruptedly entered OK；

K. remove and close wastewater influent pump (1) and H₂O₂Effluent trough in the light electrolysis unit of dosing pump (2), by light electrolysis list Micro-electrolysis reaction layer in member is taken out successively, then is sequentially placed into new micro-electrolysis reaction layer, and effluent trough is positioned over into light electrolysis list In member, enabled when in case the light electrolysis unit being used next time is stopped transport, maintenance or module type filler (4-15) have used.

A kind of 9. user of multistage light electrolysis-Fenton's reaction device of module type iron carbon filler according to claim 8 Method, it is characterised in that the micro-electrolysis reaction layer is made up of supporting plate and module type filler (4-15), is set up in parallel in supporting plate There are 600~1800 module type fillers (4-15), described module type filler (4-15) is held in the palm by laminal filter (4-15-1) and PVC Frame (4-15-2) forms, and described PVC brackets (4-15-2) are cuboid-type, built-in neck, described laminal filter (4-15- 1) it is inserted vertically into neck；

The mass fraction of each component and mesh number are respectively in described laminal filter (4-15-1)：

Cast iron or pig scrap：55~60 parts, 50~60 mesh；

Coke blacking：30~35,60~70 mesh；

Copper powder：5~10,50~60 mesh；

Binding agent：3~5；

Binding agent includes fine sand and portland cement, mass ratio 1:2~3；

After high pressure is compressing, enter stove nitrogen charging high-temperature calcination shaping, temperature is：1050~1200 DEG C, the firing time is：4~5 Hour.