CN108164056A - Aniline alkaline waste water treatment method - Google Patents
Aniline alkaline waste water treatment method Download PDFInfo
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- CN108164056A CN108164056A CN201711500541.0A CN201711500541A CN108164056A CN 108164056 A CN108164056 A CN 108164056A CN 201711500541 A CN201711500541 A CN 201711500541A CN 108164056 A CN108164056 A CN 108164056A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
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Abstract
The processing method of aniline alkaline waste water, it is related to technical field of waste water processing, aniline alkaline waste water is processed using quick ion conductor film electrochemical apparatus and two-stage fast-ionic conductor granule electrode electrochemical appliance, except having the characteristics of Conventional electrochemical, as function is more, capacity usage ratio height, process control, environment compatibility are high, economical and practical outer, pass through a series of electrochemical process in double quick ion conductor anode membrane and fast-ionic conductor granule electrode electrochemical reaction appts, achieve the purpose that remove Pollutants in Wastewater, COD removal rates reach more than 50~95%.
Description
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of processing method of aniline alkaline waste water.
Background technology
Benzene and nitric acid occur nitration reaction and crude benzol amine alkaline waste water are made under sulfuric acid catalysis effect.Aniline alkaline waste water
(NB) it is a kind of important industrial chemicals and intermediate, can be used for dyestuff, pesticide, plastic additive, detergent etc..Aniline alkalinity is given up
Water (NB) extremely difficult biodegradation into after water body, can cause the long-term severe exacerbation of water quality, be 58 kinds that China determines preferential
One of toxic chemical of control.Crude benzol amine alkaline waste water removes the sulfuric acid of deentrainment through pickling, then removes nitration reaction through alkali cleaning
By-product-triphenylamine alkaline waste water phenol, the aniline alkaline waste water after overpickling and alkali cleaning enters stripper, removes aniline alkali
Aniline is made by hydrogenation reaction in excessive benzene, qualified aniline alkaline waste water in property waste water.Crude benzol amine alkaline waste water alkali cleaning is given up
Water enters thermal splitting system, and the water outlet of the system is known as aniline alkaline waste water (i.e. thermal cracking waste water), and the waste water component complexity is simultaneously
It is difficult to biodegradation, it is necessary to after pretreatment, then be mixed with other waste water and carry out subsequent processing.
At present, there are many oxidation degradation method in relation to aniline alkaline waste water both at home and abroad, such as ozone oxidation degradation, UV-
TiO2 catalysis oxidations, UV-Fenton oxidative degradations etc., but there are different journeys in economic and technical control etc. for these methods
The problem of spending, practical application are greatly affected.
Invention content
The object of the present invention is to provide a kind of processing methods of aniline alkaline waste water, are set using fast-ionic conductor membrane electrochemical
Standby and two-stage fast-ionic conductor granule electrode electrochemical appliance processes aniline alkaline waste water, and COD removal rates reach 50-95%
More than.
Present invention technical solution used for the above purpose is：The processing method of aniline alkaline waste water, including with
Lower step：
(1), aniline alkaline waste water is filtered to remove solid content, obtains cleaner liquid；
(2), the cleaner liquid that step (1) obtains is added to quick ion conductor film in quick ion conductor film electrochemical apparatus to enclose
Into waste water district, and add in sodium hydroxide, and be passed through tap water in the outside of quick ion conductor film two, fast-ionic conductor membrane electrochemical
Equipment, which is powered, carries out the catalysis reaction of fast-ionic conductor membrane electrochemical removing sodium, after reaction, the water of waste water district processing is all released, is obtained
Water outlet that treated；The FeCl of water outlet total weight 10-15% is added in the water outlet3Aqueous solution after being stirred to react 30min, adds
Enter to be discharged the polyacrylamide solution of total weight 0.1%, stir 5min, stand reaction precipitation 2h, take supernatant liquid filtering, must filter
Liquid I；Sediment continues to use filter-cloth filtering, obtains filtrate II, and filtrate I and filtrate II are merged, obtain filtered fluid；
(3), the filtered fluid that step (2) obtains is added to two of level-one fast-ionic conductor granule electrode electrochemical appliance
In cathode chamber, level-one fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electrochemical degradation
Processing water after processing time arrives, in the case where not powering off from the lower end of anode chamber is all released, will released by pollutant process
Processing water in add in processing water total weight 10%FeCl3Aqueous solution after being stirred to react 30min, adds in processing water total weight
0.1% polyacrylamide solution stirs 5min, stands reaction precipitation 2h, takes supernatant liquid filtering, obtain filtered fluid；Sediment can
Continue to obtain filtered fluid with filter-cloth filtering, the filtered fluid handled twice is merged；
(4), the filtered fluid after the merging for obtaining step (3) adds in two level fast-ionic conductor granule electrode electrochemical appliance
Two cathode chambers in, two level fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electrification
Degradation of contaminant processing is learned, after processing time arrives, is all released processing water from the lower end of anode chamber in the case where not powering off,
The lye pH adjustment value in two outside of quick ion conductor film in quick ion conductor film electrochemical apparatus will be added in the processing water of releasing extremely
6-7 stirs 5min, stands reaction 25min, reprecipitation or filtering；Supernatant after precipitation can qualified discharge, each processing section
Generated sludge can add in a combust in coal and handle.
Wherein, in step (1), aniline alkaline waste water is filtered removing solid by settling pool and filter successively
Object.
In the present invention, in step (2), the energization of quick ion conductor film electrochemical apparatus carries out fast-ionic conductor membrane electrochemical and takes off
In sodium catalytic reaction process, electric current 15-20A, reaction time 30min all release the water of waste water district processing after reaction,
Treated water outlet, the pH value of water outlet is 8-13.
In the present invention, in step (3), level-one fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor
In granule electrode electrochemical degradation pollutant process, electric current 9-15A, residence time 60min；Processing water water outlet pH value be
5-7。
In the present invention, two level fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electricity
In chemical degradation pollutant process, electric current 6-12A, residence time 30-60min, the water outlet pH value for handling water are 2-5.
Wherein, quick ion conductor film electrochemical apparatus includes reaction kettle I, and fixed in reaction kettle I there are two be arranged in parallel
Quick ion conductor film is folded in interlayer inside porous clamping plate I, each porous clamping plate I, the inner cavity of reaction kettle I is divided successively
For mutual disconnected sodium hydroxide area I, waste water district and sodium hydroxide area II；Wherein, the waste water between two porous clamping plate I
Fast-ionic conductor anode is equipped in area, is divided in the sodium hydroxide area I and sodium hydroxide area II in two porous two outsides of clamping plate I
It She You not cathode.
Wherein, level-one fast-ionic conductor granule electrode electrochemical appliance and two level fast-ionic conductor granule electrode electrochemistry dress
The structure put is identical, and including reaction kettle II, fixed in reaction kettle II there are two the porous clamping plate II being arranged in parallel, each porous
Diaphragm is folded in interlayer inside clamping plate II, the inner cavity of reaction kettle II is divided into mutual disconnected cathode chamber I, anode successively
Room and cathode chamber II are filled with granule electrode in cathode chamber I, anode chamber and cathode chamber II；Wherein, positioned at two porous clamping plates
Fast-ionic conductor anode is equipped in anode chamber between II, cathode chamber I and cathode chamber positioned at two porous two outsides of clamping plate II
Cathode is respectively equipped in II.
Advantageous effect：To fast-ionic conductor, aniline alkaline waste water drops in double anode membranes and the oxidation of fast-ionic conductor electrochemical techniques
Effect carries out development test, the results showed that, in cathodic region, amido is up to 98%, and anode region does not change substantially, because on phenyl ring
Nitro be strong electron-withdrawing group group, it is difficult to aoxidized, amido electrochemical oxidation index be much larger than nitro the reason of, therefore, work as nitro
It is reduced to after amido again through fast ion electrode oxidative degradation, ultrahigh in efficiency.Using double quick ion conductor anode membrane and fast ion
Conductive particle electrode technology oxidative degradation aniline alkaline waste water, COD (COD) removal rate of waste water are higher.In the present invention
Under the conditions of, the COD of waste water is except rate is by Water Temperature very little；Aniline alkaline waste water is handled using conditions above, COD removal rates are up to
50-95% level above.
Double quick ion conductor anode membrane and fast-ionic conductor granule electrode electrochemical redox edman degradation Edman, it is traditional electric except having
The characteristics of chemical, if function is more, capacity usage ratio height, process control, environment compatibility are high, economical and practical outer, by double quick from
A series of electrochemical process in sub- conductor anode membrane and fast-ionic conductor granule electrode electrochemical reaction appts, reaches removal waste water
The purpose of middle pollutant.
Description of the drawings
Fig. 1 is the process chart of aniline alkaline waste water of the present invention；
Fig. 2 is the schematic diagram of quick ion conductor film electrochemical apparatus of the present invention；
Fig. 3 is level-one fast-ionic conductor granule electrode electrochemical appliance of the present invention or two level fast-ionic conductor granule electrode electricity
The schematic diagram of chemical devices；
Fig. 4 is current density experimental result picture；
Fig. 5 is water outlet pH value and COD removal rate relational graphs；
Fig. 6 is pretreatment influent quality；
Fig. 7 is the removal rate of degradation of different electrochemical reaction times COD；
Fig. 8 to Figure 13 is water treatment experimental result of the present invention；
Figure 14, Figure 15 are TDZ water inlet primary effluent aniline alkaline waste water analysis of experiments data records；
Figure 16 is TDZ water inlet secondary effluent aniline alkaline waste water analysis of experiments data records；
Figure 17 is aniline alkaline waste water analysis of experiments data record；
Figure 18 is HCF treatment effect results.
Specific embodiment
Technological means, technical characteristic and purpose to realize the present invention are easy to understand, with reference to specific embodiment
The present invention is further explained, but scope of the present invention is not limited to the range described in specific embodiment.
The processing method of aniline alkaline waste water of the present invention has been applied to the fast ion of quick ion conductor film electrochemical apparatus, level-one
Conductive particle electrode electro Chemical device and two level fast-ionic conductor granule electrode electrochemical appliance, wherein, as shown in Fig. 2, soon from
Sub- electrically conductive film electrochemical apparatus includes reaction kettle I, is fixed in reaction kettle I there are two the porous clamping plate I being arranged in parallel, each porous
Quick ion conductor film is folded in interlayer inside clamping plate I, the inner cavity of reaction kettle I is divided into mutual disconnected hydroxide successively
Sodium area I, waste water district and sodium hydroxide area II；Wherein, fast-ionic conductor is equipped in the waste water district between two porous clamping plate I
Anode is respectively equipped with cathode in the sodium hydroxide area I and sodium hydroxide area II in two porous two outsides of clamping plate I.Wherein, soon
Ion conductor anode 500mm × 250mm；316 stainless steel cathode 500mm × 250mm, are opened by fast-ionic conductor anode membrane two and are divided into
1 anode chamber and 2 cathode chambers.
As shown in figure 3, level-one fast-ionic conductor granule electrode electrochemical appliance and two level fast-ionic conductor granule electrode electricity
The structure of chemical devices is identical, fixed there are two the porous clamping plate II being arranged in parallel in reaction kettle II including reaction kettle II, often
Diaphragm is folded in interlayer inside a porous clamping plate II, the inner cavity of reaction kettle II is divided into mutual disconnected cathode chamber successively
I, anode chamber and cathode chamber II are filled with granule electrode in cathode chamber I, anode chamber and cathode chamber II；Wherein, positioned at more than two
Fast-ionic conductor anode is equipped in anode chamber between hole clip plate II, positioned at two two outsides of porous clamping plate II cathode chamber I and
Cathode is respectively equipped in cathode chamber II.Wherein, fast-ionic conductor anode 500mm × 250mm；316 stainless steel cathode 500mm ×
250mm is opened by fast-ionic conductor reticular membrane two and is divided into 1 anode chamber and 2 cathode chambers, and each fast ionizing particle electrode in room is divided
Every being not communicated with, cathode chamber filling fast-ionic conductor granule electrode.Wherein, cathode chamber I, anode chamber and cathode chamber II be filled with soon from
Sub- conductive particle electrode, cathode chamber I, anode chamber and cathode chamber II are separated by two diaphragms, and each fast ionizing particle electrode in room does not connect
It touches, water can penetrate, and pending water is entered by cathode chamber I and cathode chamber II, be discharged from anode chamber.
The processing method of the aniline alkaline waste water of the present invention, includes the following steps：
(1), aniline alkaline waste water is filtered removing solid content by settling pool and filter successively, obtains filtering
Liquid；
(2), the cleaner liquid that step (1) obtains is added to quick ion conductor film in quick ion conductor film electrochemical apparatus to enclose
Into waste water district, and add in sodium hydroxide in the outside of quick ion conductor film two, form sodium hydroxide area I and sodium hydroxide area II,
And tap water is passed through into sodium hydroxide area I and sodium hydroxide area II, quick ion conductor film electrochemical apparatus be powered, carry out soon from
Sub- conductor membrane electrochemical removing sodium catalysis reaction changes chemical constitution, and electric current 15-20A, reaction time 30min, will after reaction
The water of waste water district processing is all released, the water outlet that obtains that treated, and the pH value of water outlet is 8-13；Water outlet gross weight is added in the water outlet
Measure the FeCl of 10-15%3Aqueous solution after being stirred to react 30min, adds in the polyacrylamide solution of water outlet total weight 0.1%,
5min is stirred, reaction precipitation 2h is stood, takes supernatant liquid filtering, obtain filtrate I；Sediment continues to use filter-cloth filtering, obtains filtrate II, will filter
Liquid I and filtrate II merge, and obtain filtered fluid；Wherein, raw water adds the FeCl of 15% weight before cracking3Aqueous solution, raw water adds after cracking
The FeCl of 8% weight3Aqueous solution；Water addition polymerization acrylamide aqueous solution accounts for the 150mL/L of water volume before cracking before cracking, after cracking
Water addition polymerization acrylamide aqueous solution accounts for the 100mL/L of water volume after cracking；
Wherein, the upper end of waste water district is equipped with valve, until the valve is discharged, closes waste water district valve, sodium hydroxide area I
Tap water is added in sodium hydroxide area II, until sodium hydroxide area I and the valve of sodium hydroxide area II upper ends are discharged, closes hydrogen
The valve of sodium oxide molybdena area I and sodium hydroxide area II, tap water is released after being recycled to the water of 30 times of waste water, fast as two level
Ion conductor granule electrode, which is finally discharged, adjusts pH value use；
(3), the filtered fluid that step (2) obtains is added to two of level-one fast-ionic conductor granule electrode electrochemical appliance
In cathode chamber, level-one fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electrochemical degradation
Pollutant process, electric current 9-15A, residence time 60min；After processing time arrives, water will be handled in the case where not powering off
It is all released from the lower end of anode chamber, the water outlet pH value for handling water is 5-7；Processing water total weight will be added in the processing water of releasing
10%FeCl3Aqueous solution after being stirred to react 30min, adds in the polyacrylamide solution of processing water total weight 0.1%, stirring
5min stands reaction precipitation 2h, takes supernatant liquid filtering, obtain filtered fluid；Sediment can continue to obtain filtered fluid with filter-cloth filtering, will twice
The filtered fluid of processing merges；Wherein, raw water adds the FeCl of 6% weight before cracking3Aqueous solution, raw water adds 6% weight after cracking
FeCl3Aqueous solution；Water addition polymerization acrylamide aqueous solution accounts for the 110mL/L of water volume before cracking, water addition polymerization third after cracking before cracking
Acrylamide aqueous solution accounts for the 90mL/L of water volume before cracking；Water power stream is 15A before cracking, and water power stream is 13A after cracking；
(4), the filtered fluid after the merging for obtaining step (3) adds in two level fast-ionic conductor granule electrode electrochemical appliance
Two cathode chambers in, two level fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electrification
It is 6-12A, residence time 30-60min to learn degradation of contaminant processing electric current, after processing time arrives, in the case where not powering off
Processing water is all released from the lower end of anode chamber, the water outlet pH value for handling water is 2-5；To be added in the processing water of releasing soon from
The lye pH adjustment value in two outside of quick ion conductor film stirs 5min, stands reaction to 6-7 in sub- electrically conductive film electrochemical apparatus
25min, reprecipitation or filtering；Supernatant after precipitation can qualified discharge, sludge can add in coal caused by each processing section
In a combust handle；Wherein, water power stream is 12A before cracking, and water power stream is 10A after cracking；Through two level fast-ionic conductor particle
Clear liquid of the 2nd section of the electrode assembly processing water outlet through settling or filtering, then with quick ion conductor film electrochemical appliance cathodic region output
Alkaline cathode liquid adjust pH value to 6-7.
In process above flow, the design parameter during processing aniline alkaline waste water can refer to following analysis of experiments reports
It accuses.
It, can also be by the FeCl in each stage in process above flow3Aqueous solution replaces with the industry that mass concentration is 5g/L
Grade sodium chloride.
In the present invention, aniline alkaline waste water, raw water is diluted to 1: 50 (volume ratio)；Test equipment is COD analyzers, including
The special heating digestion devices of HE99125 types COD and the special spectrophotometers of ET99109 types COD.
It is utilized respectively industrial grade sodium chloride, the FeCl that mass concentration is 5g/L3Aqueous solution to aniline alkaline waste water at
Reason, experimentation and Comparative result are as follows：
Handle water：120t/d, pretreatment influent quality below figure 6.
First, sodium chloride addition experiment：Waste water 13L after cracking is taken, pH value measure, COD before being tested waste watercrIt measures.
Level-one fast-ionic conductor granule electrode electrochemical decomposition device anode is added after waste water 13L is added in the dissolving of 3 8g/L sodium chloride
Room, remainder, which is added in sink, makees recirculated water；It is transferred to certain electric current and carries out electrochemical decomposition experiment.Investigate different electricity
COD under stream, processing time, pH value conditioncrRemoval rate.
2nd, ferric trichloride addition experiment：Waste water 13L after cracking is taken, pH value measure, COD before being tested waste watercrIt surveys
It is fixed.Level-one fast-ionic conductor granule electrode electrochemical decomposition device anode is added after waste water 13L is added in 5 15g/L dissolvings
Room, remainder, which is added in sink, makees recirculated water；It is transferred to certain electric current and carries out electrochemical decomposition experiment.Investigate different electricity
COD under stream, processing time, pH value conditioncrRemoval rate.
3rd, the influence of time, electric current：During fast-ionic conductor electrochemical degradation, the increase of COD removal rates at any time
And increase, fast-ionic conductor electrochemistry level-one degradation 60minCOD, removal reaches 70%；Two level 60minCOD, removal rate are
95% or so.During fast-ionic conductor electrochemical degradation constantly cathodic region, anode are migrated into the R+ of anode region cations
R anion in area are constantly aoxidized, and fast-ionic conductor oxidation in anode region generates oxide species and is also on the increase, the degradation of waste water
Amount increases therewith, the increase of COD removal rates；And fast-ionic conductor electrochemical degradation is reacted to certain time, due to the concentration of waste water
It reduces, polarization phenomena occur for electrode, so as to reduce degradation efficiency.
It is 8mA/cm in current density2, after the common 60min processing of level-one, COD 8000mg/L.According to experiment COD degradation
Rate is small with pH value variation, there is redox current and residence time compared with Important Relations, but when every grade of residence time is more than 90min
When degradation rate it is very slow, most optimal retention time be every grade of 60min, pH value is between 2-3.
Fast-ionic conductor electro-chemical water treatment process has COD solvable and insoluble in various water preferable removal effect
Fruit can adjust technique according to different water quality and acid-base value, determine best operating current, and COD concentration is high under normal circumstances
When electric current it is more relatively large, but COD removal rates are also higher, and disposable removal rate is up to more than 70%.It is and relatively low to COD concentration
When, electric current is relatively small, but this water quality is a kind of water quality of the extremely difficult decomposition of COD relatively, and often COD removal rates are all relatively low, and one
As 60% or so.
Wherein, the influence experimental design of current density is as follows：Waste water is added between the mass concentration 5g/L of NaCl, pole plate
10cm, anode region quality waste water COD concentration 14000mg/L, initial pH for 13, do not stir.Under conditions of change current density
Fast ion electrochemical degradation reaction is carried out, timing sampling analysis measures, condition：Conduction time 60min；The results are shown in Figure 4.By
Fig. 4 is it is found that in the range of certain time, and with the increase of electric current, COD degradation speed is accelerated in waste water, and treatment effeciency increases.Increase
High current can accelerate the progress of electrolytic process, accelerate the release of electronics, and H+ is promoted to be transformed into H；Increase electrode surface and master
Proton concentration gradient in liquid solution, and the mass transfer rate of fast-ionic conductor material for making clothes electrode surface can be increased.When electric current is more than 25A
When, pollutant (such as COD) the electrochemical degradation process of aniline alkaline waste water is influenced smaller by size of current, this is primarily due to
Side reaction 2H++2e → H that electrochemical process generates2, dramatically speeded up as current density increases its reaction rate, make aniline alkali
Property waste water be difficult to quickly contact and be reduced with electrode surface, at this point, can from fast ion unit be discharged pH value still find out for alkalinity.
Wherein, the influence experimental design of additive level is as follows：Test voltage is 9V, electric current 13A, timing sampling analysis
Measure, result of the test show when reagent additive amount be more than it is a certain amount of or less than it is a certain amount of when, the removal rate of COD can all have one
Fixing is rung.
When wherein, using sodium chloride as additive, influence such as Fig. 7 of electrochemical reaction time.
When the mass concentration of sodium chloride is 5g/L it can be seen from Fig. 6 and Fig. 7, waste water COD reaction rate amount is big, this master
If due to increasing with electrolyte content, the conductivity increase of solution, conductive capability enhances, and proton is migrated from solution main body
Rate to cathode surface increases, and the hydroperoxyl radical H of more strong reducing power electrification subbase group can be generated, so as to accelerate
The degradation rate of pollutant in solution.After electrolyte content reaches certain value, because of the Interaction enhanced between ion, ion fortune
Dynamic to be affected, conductivity declines.Meanwhile but saprobia structures in Cl too high levels, it will inhibit and poison microorganism,
It is unfavorable for wastewater biochemical processing.Thus under existing experimental condition, the mass concentration for determining the addition of sodium chloride electrolysis matter is 5g/L.
Wherein, the influence experimental design of pH value is as follows：Under experimental condition of the sodium chloride for additive：Add sodium chloride matter
Concentration 5g/L, pole plate spacing 10cm, voltage 10V are measured, flows close 15A standing tests, conduction time 60min, timing sampling analysis
It measures, as a result such as Fig. 5.The result shows that with the reduction of pH, the degradation efficiency of COD gradually increases, and apparent reaction speed gradually adds
Soon, for pH value at 2, COD removal rates are up to 85%, but, optimal pH selection 3-4 also more to water outlet height-regulating pH value consumption catholyte.
The basic principle of organic pollution in fast-ionic conductor granule electrode electrochemical reduction processing aniline alkaline waste water
It is the direct-reduction of granule electrode cathode and indirect reduction and the direct oxidation of granule electrode anode and indirect oxidation, that is, has
Machine pollutant is obtained electronics on cathode and direct reduction reactor occurs and is generated using fast-ionic conductor granule electrode cathode surface
Strong reduction activation substance make organic matter occur reduction transformation.When aniline alkaline waste water (NB) content is higher, mass transfer can be passed through
Absorption leads granule electrode cathode surface in fast ion, and obtains electronics and direct in fast-ionic conductor granule electrode cathode surface
Reduction.As NB contents reduce, the probability that direct reduction reactor occurs on cathode is reduced, and processing procedure is mostly between cathode
Connect reduction reaction.It observes there is bubble formation in cathode surface simultaneously, is studied according to forefathers, the final product of evolving hydrogen reaction is molecule
Hydrogen, but in fast-ionic conductor granule electrode cathode surface, 2 hydrated protons are considerably less in the chance that same place discharges, proton
The initial product of reduction reaction is H, and H has high chemism can be with the knot of the organic pollution in reducing solution
Structure, so as to improve degradation rate of the fast-ionic conductor granule electrode to water pollutant.
It is added in after fast-ionic conductor film process in fast-ionic conductor granule electrode electrochemical appliance, COD mass concentrations are
14000mg/L gives up before cracking after aniline alkaline waste water 13L or the aniline alkaline waste water cracking that mass concentration is COD5000mg/L
Water 13L.Voltage 10V, electric current 15A, interpolar is away from 10cm, initial pH on wastewater 14, and additive is sodium chloride 5g/L, static examination
It tests, timing water sampling Analysis for CO D, observes the degradation situation of COD under the differential responses time.The product of aniline (AN) is seen that there is from experiment
It is tired, it can therefore be concluded that in the AN of cathodic region generation, other substances are then oxidized in anode region, so as to improve waste water
Biodegradability.Preceding 1h, theoretical reasoning are gradually decreased for the amount in cathodic region aniline alkaline waste water (NB), and the amount of aniline (AN) is gradual
Increase.After anodic-cathodic is exchanged, the content of NB does not change substantially, and the content of AN reduces rapidly.In conclusion on phenyl ring
Nitro be strong electron-withdrawing group group, it is difficult to aoxidized；And nitro is then easier to be aoxidized after cathodic reduction is amido；This be by
It is far longer than nitro in the electrochemical oxidation index of amido.
It being found during the experiment of aniline alkaline waste water COD removal efficiency, addition NaCl can improve the conductivity of aqueous solution,
Cl, ClO can be generated simultaneously2, the oxidizing species such as HClO, have indirect degradation effect to COD in water, but its electrochemical catalysis is imitated
Fruit can not show a candle to FeCl3.Because it is still to exist in the form of NaCl that NaCl, which is added in waste water, meanwhile, increase sodium in waste water from
Son, since sodium ion is higher in aniline alkaline waste water, waste water is in strong basicity, and pH value is in 13-14 or so, electricity most in this way
For the electrolysis and migration of sodium ion, lead to reduction-oxidation energy of the fast-ionic conductor granule electrode device under the conditions of particular charge
Power reduces.After aniline alkaline waste water adds in FeCl3 aqueous solutions, FeCl3It ionizes as Fe (OH)2、Fe2+, while generate ClO2、
The oxidizing species such as HClO have good degradation to COD in water.Fe(OH)2Have to suspended matter in water and colloidal substance
Very strong flocculation, through this pretreated aniline alkaline waste water haze reduction, to fast-ionic conductor granule electrode except have compared with
Outside good protective effect, while the resistance of water body is reduced, also reduce energy consumption.Fe2+In the electricity of fast-ionic conductor granule electrode
There is extremely strong catalysis under chemical action, the electrochemical degradation performance of fast-ionic conductor granule electrode can be improved.Due to soon from
Sub- conductive particle electrode has extremely low analysis oxygen performance, makes Fe2+In fast-ionic conductor granule electrode cathodic region, catalysis generates more
H·、HO·、H2O2Etc. strong oxidizing properties and strong reducible agent, there is good removal to act on to pollutants such as the COD in water, formed
Electrochemical catalysis and Fe2+The double degradation functions of catalysis, make electrochemical appliance greatly improve the removal rate of water pollutant.Cause
This, Fe2+Have the electrochemical catalysis function of improving fast-ionic conductor granule electrode, also preferably flocculation turbidity removal effect,
Significant effect adds NaCl better than in aniline alkaline waste water.The degradation for the accelerating water pollutant speed of ferric trichloride
Rate improves electrochemical utilization rate, reduces energy consumption and operating cost.
It is a kind of effective processing NB (aniline that extrinsic current, which directly acts on fast-ionic conductor granule electrode electrochemical degradation method,
Alkaline waste water) waste water method, through quick ion conductor film electrochemical apparatus removing sodium change aniline alkaline waste water water quality structure, water outlet
Using water after addition 10% ferric chloride aqueous solutions processing, it is handled through level-one fast-ionic conductor granule electrode electrochemical appliance
COD removal rates can reach 50-80%, will through level-one fast-ionic conductor granule electrode electrochemical appliance treated water outlet again through two
Its COD removal rate of grade fast-ionic conductor granule electrode electrochemical appliance treated water can reach more than 70-95%；Pass through experiment
Determine that best reaction condition is：Initial pH on wastewater value is 8-13, and the electric current through quick ion conductor film electrochemical apparatus is 15
20A, water outlet pH value are 6-9, residence time 30min；Level-one fast-ionic conductor granule electrode electrochemical appliance current density is 9-
10A, water inlet initial pH value are 6-9, are discharged pH value 5-7, residence time 60min；Two level fast-ionic conductor granule electrode electrochemistry
Device current density is 6 8A, and water inlet initial pH value is 6-9, and water outlet pH value is 3-5, residence time 30-60min.Again through soon from
Sub- conductor film device cathode water tune pH value is 6-7, is finally discharged COD removal rates as 80-99%.
In the present invention, it is preferred that electrochemical reaction process voltage controls 8-15V, and current control is in 6-9mA/cm2；Electrification
Reaction process time control is learned in quick ion conductor film electrochemical apparatus 30min, level-one fast-ionic conductor granule electrode electrochemistry
Device 60min, two level fast-ionic conductor granule electrode electrochemical appliance 30min.
The present invention makees anode with fast-ionic conductor coated electrode, makees cathode with 316 stainless steels and special special fast ion is led
Body anode membrane, fast-ionic conductor granule electrode composition electrochemical decomposition system.The nitre without cracking of offer in benzene waste water and is split
Aniline alkaline waste water after solution has been made dirty in quick ion conductor film and fast-ionic conductor granule electrode electrochemistry electrolysis degradation water
Contaminate object.
Using the processing method of the present invention, water treatment experiment is carried out：Wherein, water treatment experiment was carried out in 3rd in August,
Handling result is as shown in figure 8, the fast ion anode membrane separation test of aniline alkaline waste water, both sides cathode are put into tap water, grading electrode
It is put into waste water；Aniline alkaline waste water fast-ionic conductor anode membrane separation test was carried out in 5th in August, handling result is as shown in Figure 9；8
The moon 13 carried out aniline alkaline waste water fast-ionic conductor anode membrane separation test, and both sides cathode is put into tap water, and grading electrode is put into
Waste water 13L, handling result are as shown in Figure 10；Aniline alkaline waste water fast-ionic conductor anode membrane separation test is carried out in August 14 days, two
Side cathode is put into tap water, and grading electrode is put into waste water 13L, and handling result is as shown in figure 11；August aniline alkaline waste water on the 15th is fast
Ion conductor anode membrane device separation test, both sides cathode are put into tap water, and grading electrode is put into waste water, fast-ionic conductor anode membrane dress
It puts separation water outlet and adds in first order fast-ionic conductor granule electrode and second level fast-ionic conductor granule electrode device, handling result
As shown in figure 12；August aniline alkaline waste water fast-ionic conductor anode membrane device separation test on the 30th, both sides cathode are put into tap water,
Grading electrode is put into waste water, and the separation water outlet of fast-ionic conductor anode membrane device adds in first order fast-ionic conductor granule electrode and second
Grade fast-ionic conductor granule electrode device, handling result are as shown in figure 13.Other not described contents of the invention belong to the prior art.
Water treatment is carried out using the process flow chart of Fig. 1 of the present invention：
First, TDZ water controls machine is discharged
1st, water intaking control machine water outlet 100L adds in bucket, and diaphragm apparatus cathode chamber fills tap water, and electric current is adjusted to 18A, opens
Water pump is intake from the anode chamber of diaphragm apparatus；
2nd, diaphragm water outlet adds in the liquor ferri trichloridi of the concentration 10% of 10% percentage, adjusts pH value to 7, adds in 2%
Polyacrylamide be allowed to precipitate；
3rd, supernatant is taken to second bucket, and electric current is adjusted to 13A, water pump is opened, respectively from the moon of level-one fast-ionic conductor
Pole room is intake；
4th, primary effluent adds in the liquor ferri trichloridi of 10% concentration 10%, adjusts pH value to≤5, is allowed to natural sedimentation；
5th, supernatant is taken to third bucket, and electric current is adjusted to 10A, water pump is opened, respectively from the moon of level-one fast-ionic conductor
Pole room is intake.
Experiment reagent：Mass concentration is 10% ferric trichloride, and cation is 5/10000ths polyacrylamide；
Treating capacity：Diaphragm apparatus is 24L/h, and the fast ion unit of level-one is 13L/h, and the fast ion unit of two level is 13L/h.
Experimental phenomena：After diaphragm water outlet adds in ferric trichloride, there is a gas generation, reaction is violent, and foam is very big, pH value for≤
When 5, adding in polyacrylamide will not flocculate.When pH value is adjusted to 6-7, there is flocculate generation, and precipitate rapidly, there is bubble production therewith
Raw, floccule body can float therewith, then flocculate into big group again to top, and can precipitate again.According to experimental data, it is discharged into
Acidity adds in a concentration of 3% alkaline solution neutralization.
2nd, TDZ water controls machine is intake
Experimental procedure is consistent with the water outlet of TDZ, and dosage 15%, polyacrylamide solution 2%, electric current, voltage are not
Become.
Experimental phenomena：After adding in liquor ferri trichloridi, there is minimum gas generation, be not very acutely, to there is a small amount of bubble.It adds in
After polyacrylamide, there is flco generation, after static, supernatant no suspended substance.
Wherein, Figure 14, Figure 15 are TDZ water inlet primary effluent aniline alkaline waste water analysis of experiments data records；Figure 16 is TDZ
Water inlet secondary effluent aniline alkaline waste water analysis of experiments data record；Figure 17 is aniline alkaline waste water analysis of experiments data record
(TDZ water inlets, water outlet, HCF water outlets)；Figure 18 is HCF treatment effect results.
Above example makes in order to illustrate technical scheme of the present invention, and the purpose is to be to enable those skilled in the art
Understand present disclosure and be practiced, but do not limited the scope of the invention with this.Every reality according to the present invention
The equivalent variation or modification that matter content is made should all be covered within the scope of the present invention.
Claims (7)
1. the processing method of aniline alkaline waste water, which is characterized in that include the following steps：
(1), aniline alkaline waste water is filtered to remove solid content, obtains cleaner liquid；
(2), the cleaner liquid that step (1) obtains is added to what quick ion conductor film in quick ion conductor film electrochemical apparatus surrounded
Waste water district, and sodium hydroxide is added in, and be passed through tap water in two outside of quick ion conductor film, quick ion conductor film electrochemical apparatus
It is powered and carries out the catalysis reaction of fast-ionic conductor membrane electrochemical removing sodium, after reaction, the water of waste water district processing is all released, must be handled
Water outlet afterwards；The FeCl3 aqueous solutions of water outlet total weight 10~15% are added in the water outlet, after being stirred to react 30min, are added in out
The polyacrylamide solution of water total weight 0.1% stirs 5min, stands reaction precipitation 2h, takes supernatant liquid filtering, obtain filtrate I；
Sediment continues to use filter-cloth filtering, obtains filtrate II, and filtrate I and filtrate II are merged, obtain filtered fluid；
(3), the filtered fluid that step (2) obtains is added to two cathodes of level-one fast-ionic conductor granule electrode electrochemical appliance
In room, level-one fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out the pollution of fast-ionic conductor granule electrode electrochemical degradation
Object processing after processing time arrives, all releases processing water from the lower end of anode chamber in the case where not powering off, by the place of releasing
It manages and processing water total weight 10%FeCl3 aqueous solutions is added in water, after being stirred to react 30min, add in processing water total weight 0.1%
Polyacrylamide solution stirs 5min, stands reaction precipitation 2h, takes supernatant liquid filtering, obtain filtered fluid；Sediment can continue with filter
Cloth filters to obtain filtered fluid, and the filtered fluid handled twice is merged；
(4), the filtered fluid after the merging for obtaining step (3) adds in the two of two level fast-ionic conductor granule electrode electrochemical appliance
In a cathode chamber, two level fast-ionic conductor granule electrode electrochemical appliance, which is powered, carries out fast-ionic conductor granule electrode electrochemistry drop
Pollutant process is solved, after processing time arrives, processing water from the lower end of anode chamber is all released in the case where not powering off, will be put
The lye pH adjustment value in the outside of quick ion conductor film two in quick ion conductor film electrochemical apparatus is added in the processing water gone out to 6~7,
5min is stirred, stands reaction 25min, reprecipitation or filtering；Supernatant after precipitation can qualified discharge, each processing section produced
Raw sludge can add in a combust in coal and handle.
2. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：In step (1), by aniline alkalinity
Waste water is filtered removing solid content by settling pool and filter successively.
3. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：In step (2), fast-ionic conductor
Membrane electrochemical equipment, which is powered, to be carried out in fast-ionic conductor membrane electrochemical removing sodium catalytic reaction process, and electric current is 15~20A, during reaction
Between for 30min, the water of waste water district processing is all released after reaction, the water outlet that obtains that treated, the pH value of water outlet is 8~13.
4. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：In step (3), the fast ion of level-one
Conductive particle electrode electro Chemical device, which is powered, to carry out in fast-ionic conductor granule electrode electrochemical degradation pollutant process, and electric current is
9~15A, residence time 60min；The water outlet pH value for handling water is 5~7.
5. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：In step (4), the fast ion of two level
Conductive particle electrode electro Chemical device, which is powered, to carry out in fast-ionic conductor granule electrode electrochemical degradation pollutant process, and electric current is
6~12A, residence time are 30~60min, and the water outlet pH value for handling water is 2~5.
6. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：Fast-ionic conductor membrane electrochemical is set
It is standby to include reaction kettle I, it is fixed in reaction kettle I there are two the porous clamping plate I being arranged in parallel, the interlayer inside each porous clamping plate I
In be folded with quick ion conductor film, by the inner cavity of reaction kettle I be divided into successively mutual disconnected sodium hydroxide area I, waste water district and
Sodium hydroxide area II；Wherein, fast-ionic conductor anode is equipped in the waste water district between two porous clamping plate I, positioned at two
Cathode is respectively equipped in the sodium hydroxide area I and sodium hydroxide area II in porous two outsides of clamping plate I.
7. the processing method of aniline alkaline waste water as described in claim 1, it is characterised in that：Level-one fast-ionic conductor particle electricity
Pole electrochemical appliance is identical with the structure of two level fast-ionic conductor granule electrode electrochemical appliance, including reaction kettle II, reaction
Fixed in kettle II there are two the porous clamping plate II being arranged in parallel, and are each folded with diaphragm in the interlayer inside porous clamping plate II, will
The inner cavity of reaction kettle II is divided into mutual disconnected cathode chamber I, anode chamber and cathode chamber II, cathode chamber I, anode chamber and the moon successively
Granule electrode is filled in pole room II；Wherein, fast-ionic conductor is equipped in the anode chamber between two porous clamping plate II
Anode is respectively equipped with cathode in the cathode chamber I and cathode chamber II in two porous two outsides of clamping plate II.
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