CN108298682A - A kind of anaerobic membrane electricity biological treatment of novel low-intensity organic wastewater - Google Patents
A kind of anaerobic membrane electricity biological treatment of novel low-intensity organic wastewater Download PDFInfo
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- CN108298682A CN108298682A CN201810097566.9A CN201810097566A CN108298682A CN 108298682 A CN108298682 A CN 108298682A CN 201810097566 A CN201810097566 A CN 201810097566A CN 108298682 A CN108298682 A CN 108298682A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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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
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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
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
A kind of anaerobic membrane electricity biological treatment of novel low-intensity organic wastewater, it includes the following steps：Carbon nanotube after acidification is loaded to through vacuum filtration on glass fibre membrane, and micro-filtration conductive film is made；The Anaerobic treatment technique based on upflow anaerobic sludge blanket reactor, membrane bioreactor are flat between its suspended sludge area and three-phase separation area, form anaerobic membrane integral biological treatment process；Micro-filtration conductive film is introduced as electrode, forms Novel anaerobic film electricity biological treatment.The parameter for regulating and controlling reaction unit includes hydraulic detention time, temperature, voltage etc..The present invention can reach following effect：Conductive film plays film retention and membrane electrode effect simultaneously, strengthens effluent quality, improves methane production, synchronizes alleviation fouling membrane in situ, extends conductive film service life.The treatment process has many advantages, such as that cost of investment is few, floor space is small, easy to operate, improvement effect is notable, can be applied to the low-intensity organic wastewaters such as processing city domestic sewage.
Description
Technical field
The present invention relates to a kind of Anaerobic treatment techniques of city domestic sewage.
Background technology
City domestic sewage generally uses aerobic biological treatment process, power consumption high.It is anti-with up-flow anaerobic sludge blanket
The Anaerobic Microbiological Treatment Technology that Ying Qiwei is represented, since it is strong with anti impulsion load ability, low energy consumption, excess sludge production
Less, production biogas (main component is methane and carbon dioxide), it is easy to operate the features such as, more and more people are applied to processing
City domestic sewage.
Theoretically, Anaerobic Microbiological Treatment Technology is more suitable for handling middle and high intensity organic wastewater, and city domestic sewage
It learns oxygen demand and is generally 300~500mg/L, belong to low-intensity organic wastewater.Therefore, in order to strengthen detesting for low-intensity organic wastewater
Oxygen biological treatment effect, consideration is coupled thereto by membrane bioreactor, to improve effluent quality and methane production.I.e. by film biology
Reactor is flat on inside upflow anaerobic sludge blanket reactor between suspended sludge area and three phase separator, forms anaerobism -- film
Integral biological treatment process further retains the organic matter in sewage using the efficient retention centrifugation of biomembrane.
However, anaerobic membrane biosystem treatment process is not widely used in the processing of practical low-intensity organic wastewater, limit
Reason processed is mainly the membrane pollution problem of membrane bioreactor.Being continuously pumped into and handling with sewage, membrane bioreactor
Separation membrane surface can adsorb a large amount of microorganisms, and membrane aperture is caused to reduce, and membrane flux reduces, and then influence wastewater treatment efficiency.It passes
The fouling membrane solution of system is physico-chemical process, i.e., is backwashed by waterpower or add the modes such as chemical reagent to alleviate film
Pollution, but this undoubtedly increases technology investment cost, and by complex treatment process, it is micro- that the chemical reagent that adds can also limit anaerobism
The growth of biology leads to the reduction of useless Organic substance in water treatment effect.In addition, the waterpower of city domestic sewage anaerobic bio-treated
Residence time is generally 1~2d, and the time is longer, this also becomes a factor for limiting process engineeringization application.Therefore, simultaneously
Realize that the fouling membrane of anaerobic membrane biosystem treatment process is alleviated in situ, and the low-intensity organic wastewater in relatively low hydraulic detention time
Processing up to standard, be the key that current to solve the application of low-intensity organic wastewater anaerobic membrane biosystem treatment process limited.
Invention content
In order to realize that membrane pollution of membrane bioreactor alleviates the height with organic matter in relatively low hydraulic detention time in situ simultaneously
Effect removal, the present invention propose following technical scheme：A kind of anaerobic membrane electricity biological treatment device of low-intensity organic wastewater,
It is characterized in that：Upflow anaerobic sludge blanket reactor equipped with insulating layer ii is placed on pedestal, and its underpart is equipped with water distributor.Particle
Sludge area and suspended sludge area are set to upflow anaerobic sludge blanket reactor inner cavity from bottom to top.One end of intake pump is via pipe
Vi is inserted into intake pool and the other end is connect via pipe i, valve i with the bottom of the water distributor.It is equipped with extremely in granule sludge area
Few a pair of carbon electrode, titanium silk i connection carbon electrodes and across the through-hole i of upflow anaerobic sludge blanket reactor lower part side and
The connecting line iii of electrochemical workstation connection jaws iii is connected to tie point i.Pipe v, the connection granule sludge areas the valve v other sides
Lower part.Pressure gauge ii is connected to suspended sludge area top via valve iv and pipe iv.In upflow anaerobic sludge blanket reactor
Portion is equipped with membrane bioreactor.The membrane bioreactor bosom is equipped with conductive film, and washer is separately positioned on the upper of conductive film
Lower both sides.Titanium silk ii is connected and passes through the connecting line ii of the connection jaws i of through-hole ii and electrochemical workstation to connect with conductive film surface
It is connected to tie point ii.Upflow anaerobic sludge blanket reactor top equipped with insulating layer i be three-phase separation area, three phase separator and
Reference electrode is individually fixed in the upper cover of upflow anaerobic sludge blanket reactor.Three phase separator upper port setting collection gas port.
The top of reference electrode is connected with titanium silk iii and is connected to tie point iii with the connecting line i of electrochemical workstation connection jaws i.Pressure
Power table i is connected to the lower part of three-phase separation area through valve iii and pipe iii.The sides valve ii are through pipe ii and three-phase separation area top
Water outlet be connected and the other side is discharged into discharge bay through pipe vii.
A kind of using above-mentioned apparatus includes following process to the anaerobic membrane electricity biological treatment of low-intensity organic wastewater：
1) in draught cupboard, 10mL concentrated nitric acids are first slowly added into 250mL beakers, then along wall of cup to be slowly added to 30mL dense
Sulfuric acid, it is stirring while adding, prepare 40mL nitration mixture (volume ratios 1:3) spare.
2) to process 1) described in nitration mixture in be slowly added to particle size range be 40-60nm carbon nanotube 0.5-1.5g, side
Edged stirs, until carbon nanotube is completely dissolved in nitration mixture；Preferably, weighing 1g carbon nanotubes is dissolved in nitration mixture.
3) by process 2) in the solution that is thoroughly mixed be poured slowly into 250mL round-bottomed flasks, after being sealed with preservative film, be placed in
Heating mantle is stirred heating, and heating time is 20~30min, and temperature is controlled at 60~80 DEG C；Preferably, 80 DEG C of perseverances of selection
Warm agitating and heating 30min experiment conditions, to realize the complete acidification of carbon nanotube.After stopping heating, round-bottomed flask, air are taken out
It is cooling.
4) 1000mL beakers, built-in 800mL deionized waters are used.By process 3) in mixing in round-bottomed flask after cooling
Solution is poured slowly into wherein, stirring while adding, and deionized water is used in combination to rinse round-bottomed flask repeatedly, and flushing liquor is poured into beaker,
Until liquid is to 1000mL in beaker.Beaker is sealed with preservative film, stands 10~15h.Preferably, selection stands 15h, it can be bright
It is aobvious to observe that internal mix liquid is layered.
5) by process 4) in be layered mixed liquor supernatant liquor outwell, by be filtered by vacuum method, surplus solution is filtered
On 0.45 μm of moisture film, deionized water is used in combination to rinse beaker bottom repeatedly, continues to filter flushing liquor, until beaker bottom is not residual
Remaining black solid.
6) with spoon scrape process 5) in filter water film surface acidification after carbon nanotube, be placed in glass plate surface,
Drying drying is carried out under the conditions of 80 DEG C.It after the completion of drying, places it in beaker, stores at ambient temperature spare.
7) 0.03~0.06g processes 6 are taken) in the carbon nanotube that is dried for standby, be added in 100mL dimethylformamides, side
Edged stirs, then ultrasound 2h, makes it completely dissolved, conducting membrane material preparation solution is made.Again by the method for vacuum filtration, by 10
The preparation solution of~30mL is loaded on the glass fibre membrane of diameter 40mm.Preferably, the process using 0.05g carbon nanotubes/
(100mL dimethyl formamide solutions) conducting membrane material preparation solution carries out vacuum loading with 20mL preparation solutions/film.
8) by process 7) in film after load preparation solution be placed in 250~300 DEG C of stove and carry out 2~2.5h of high temperature sintering,
Prepare the carbon nanotube-glass fibre conductive film for completing a diameter of 40mm；Preferably, temperature programming condition setting is：Heating
Rate is 5 DEG C/min, and sintering temperature is 300 DEG C, sintering time 2h.
9) anaerobic biological treatment apparatus is started using the digested sludge for being derived from anaerobic sludge fermentation tank, makes granule sludge area
Sludge concentration reach 10~20g/L.
10) take process 8) conductive film be placed in membrane bioreactor, surface is connected with titanium silk ii, is connected by through-hole ii
It is connected to outside device.Upflow anaerobic sludge blanket reactor lower part is placed in using conductor material carbon-point, surface is connected with titanium silk i,
It is connected to outside device by through-hole i；Optimum condition：In order to realize good electric conductivity, four diameter 10mm, length are chosen
The carbon-point of 35mm is connected by titanium silk i between every carbon-point.
11) electrochemical workstation is opened, the titanium silk iii and connecting line i being connected with reference electrode are connected to tie point iii,
The titanium silk ii and connecting line ii being connected with conductive film are connected to tie point ii, and the titanium silk i and connecting line iii being connected with carbon-point are connect
In tie point i.Setting cathode potential is 0V, changes anode potential, two inter-electrode voltages of control are within the scope of 0.8~1.2V；Make
It is preferred, control voltage is 1.0V.
12) open intake pump and valve i, low-intensity organic wastewater from intake pool successively via pipe vi, pipe i, water distributor, into
Enter upflow anaerobic sludge blanket reactor lower part granule sludge area.Hydraulic detention time is controlled in 4~8h, best hydraulic retention
Between be 6h；At 25~30 DEG C, optimum temperature is 30 DEG C for temperature control.
13) valve iv is opened, the organic wastewater before conductive film retention obtains pressure before film via pipe iv surge table ii
Number；It opens valve iii and obtains number pressure after film by the processed waste water of conductive film via pipe iii surges table 1.The two
Difference, as transmembrane pressure.
14) pass through conduction under hydraulic blow effect by certain anaerobic membrane biosystem treated organic wastewater before conductive film
Film layer, into upflow anaerobic sludge blanket reactor top, three-phase separation area complete water, qi leel from.Valve ii is opened, it is up to standard
Water outlet is stored in through pipe ii, valve ii, pipe vii bleeders in discharge bay；The gas of generation through three phase separator discharger,
It is effectively collected in collection gas port.
15) measure process 14 every 12~15h) in liquid volume in discharge bay.As preferred：It measures and is discharged every 15h
Pond liquid volume.
It is this to be by the characteristics of anaerobic membrane electricity biological treatment of target object of low-intensity organic wastewater：Using upstream
Formula anaerobic mud bed reactor realizes the anaerobic bio-treated of low-intensity organic wastewater.Membrane bioreactor is coupled, composition is detested
Oxygen -- film integral biological treatment process retains the organic matter in sewage using the crown_interception that efficiently separates of biomembrane, realizes
The concentration of upflow anaerobic sludge blanket reactor lower part organic matter extends the time of contact of organic matter and anaerobe, effectively
Solve the situation not up to standard of effluent quality under the conditions of low hydraulic detention time.Carbon nanotube is a kind of novel high-strength carbon fiber
Material, the electric conductivity with metal material prepare the surface of its acidification-suction filtration-drying-dissolving back loading to membrane material
Electric conductivity is good to lead microfiltration membranes.Generally, electroactive anaerobe surface carries negative electrical charge, according to the electricity that there is a natural attraction between the sexes
Lotus principle applies anode potential that can lead micro-filtration film surface, can make its surface and the certain microorganism of internal quick adsorption, form sun
Pole biomembrane.Its advantage shows three aspects：First, the microbes of absorption reduce the porosity of microfiltration membranes, raising can be cut
The particle size range for staying organic matter realizes a wide range of concentration of organic matter, is conducive to the organic efficient of lower hydraulic detention time
Processing；Second, the microorganism of conductive film surface and internal absorption can be improved with the organic matter in enhancing degradation waste water at organic matter
Manage efficiency；Third, the electroactive anaerobe of conductive film adsorption, can optimize the electric conductivity of conductive film, coulomb effect is improved
Rate.Meanwhile the booster action of electrochemistry can also change conductive membrane property, improve its permeance property, separating property and antipollution
Performance.Therefore, the anaerobic membrane electricity biological treatment of this low-intensity organic wastewater can reach following effect：Conductive film is sent out simultaneously
Wave film retention and membrane electrode effect：The organic matter in waste water is retained, extends its time of contact with anaerobe, improves low water
Organic matter treatment effeciency under the power residence time；Anode biomembrane is quickly formed, conductive film electric conductivity is improved, strengthens water outlet water
Matter improves methane production.Electrochemistry auxiliary alleviates fouling membrane, improves membrane permeability energy and separating property, extends conductive film and uses
Service life.The technology has many advantages, such as that cost of investment is few, floor space is small, easy to operate, improvement effect is notable, can be applied to
Handle the low-intensity organic wastewaters such as city domestic sewage.
Description of the drawings
Fig. 1 is a kind of anaerobic membrane electricity biological treatment schematic device of low-intensity organic wastewater.
Fig. 2 is that a kind of anaerobic membrane electricity biological treatment of low-intensity organic wastewater occurs at hydraulic detention time (HRT)
Methane production change schematic diagram when variation.
Fig. 3 is that a kind of anaerobic membrane electricity biological treatment of low-intensity organic wastewater occurs at hydraulic detention time (HRT)
Water outlet COD (COD) change schematic diagram when variation.
Fig. 4 is that a kind of anaerobic membrane electricity biological treatment of low-intensity organic wastewater occurs at hydraulic detention time (HRT)
Delivery turbidity change schematic diagram when variation.
In Fig. 1：1, connecting line i, 2, connecting line ii, 3, electrochemical workstation, 4, connection jaws i, 5, connection jaws ii, 6, wiring
Mouthful iii, 7, connecting line ii i, 8, pipe i, 9, intake pump, 10, valve i, 11, tie point i, 12, titanium silk i, 13, through-hole i, 14,
Grain sludge area, 15, suspended sludge area, 16, washer i, 17, tie point ii, 18, titanium silk ii, 19, through-hole ii, 20, insulating layer i,
21, three phase separator, 22, three-phase separation area, 23, tie point iii, 24, titanium silk iii, 25, Ag/AgCl reference electrodes, 26, collection
Gas port, 27, pipe ii, 28, valve ii, 29, pressure gauge i, 31, pipe iii, 32, membrane bioreactor, 33, valve i ii, 34, lead
Electrolemma (working electrode), 35, valve iv, 36, pressure gauge ii, 38, pipe iv, 39, insulating layer ii, 40, carbon-point (to electrode), 41,
Pipe v, 42, valve v, 43, water distributor, 44, pedestal, 45, pipe vi, 46, intake pool, 47, discharge bay, 48, pipe vii.
Specific implementation mode
The anaerobic membrane electricity biological treatment device of this novel low-intensity organic wastewater, its main feature is that：By membrane bioreaction
32 horizontal of device is answered to be connected between upflow anaerobic sludge blanket reactor suspended sludge area 15 and three-phase separation area 22, i.e. up flow type
Anaerobic mud bed reactor is that knot circle is divided into two parts up and down with membrane bioreactor 32.Wherein, 32 or less membrane bioreactor
Mainly granule sludge area 14, low-intensity organic wastewater is successively through pipe vi-45, intake pump 9, pipe i-8, valve i-10, water distributor
43, upflow anaerobic sludge blanket reactor lower part is entered by intake pool 46, under the action of anaerobe, it is useless to carry out low-intensity
The anaerobic bio-treated of water；Low hydraulic detention time is set, and the organic matter that do not degrade in time in waste water is because of membrane bioreactor 32
Middle conductive film 34 efficiently separates crown_interception, is back to upflow anaerobic sludge blanket reactor lower part, realizes the dense of organic matter
Contracting extends the time of contact of organic matter and anaerobe, strengthens effluent quality.It is up to standard that treated that waste water passes through conductive film 34
Into upflow anaerobic sludge blanket reactor top, water, qi leel are completed from water outlet is through pipe ii-27, valve in three-phase separation area 22
Ii-28 is stored in discharge bay 47, and the gas of generation is collected in collection gas port 26.The anaerobic membrane electricity of the low-intensity organic wastewater is given birth to
The application mechanism of object treatment process is：
1, anaerobic bio-treated is carried out to low-intensity organic wastewater using upflow anaerobic sludge blanket reactor, there is energy consumption
It is low, excess sludge production is few, production biogas (main component is methane and carbon dioxide), it is easy to operate the features such as.In order to improve out
Water water quality strengthens organic matter treatment effect, considers membrane bioreactor is coupled thereto, composition anaerobism -- at film integral biological
Science and engineering skill.Microfiltration membranes efficiently separate crown_interception under, organic matter in waste water is extended organic by effectively catching and concentration
The time of contact of object and anaerobe, to effectively solve the feelings not up to standard of effluent quality under the conditions of low hydraulic detention time
Condition.
2, under normal circumstances, electroactive anaerobe surface carries negative electrical charge.By carbon nanotube loaded to microfiltration membranes table
Face is prepared leads microfiltration membranes with excellent conductive performance, according to the charge principle that there is a natural attraction between the sexes, applies in conductive film surface
Anode potential makes its surface and the certain microorganism of internal quick adsorption, forms anode biomembrane.Its advantage mainly has three：When
The microorganism of absorption reduces the porosity of microfiltration membranes, expands the particle size range that can retain microorganism, realizes a wide range of of organic matter
Concentration is conducive to the organic efficient processing under the conditions of lower hydraulic detention time；Second is that conductive film surface and inside were adsorbed
Microorganism can improve organic matter treatment effeciency with the organic matter in enhancing degradation waste water；Third, the electricity of conductive film adsorption is living
Property microorganism can optimize its electric conductivity, improve coulombic efficiency.Meanwhile the booster action of electrochemistry can also change conductive film
Characteristic improves its permeance property, separating property and antifouling property.
3, by electrochemistry booster action in upflow anaerobic sludge blanket reactor-membrane bioreactor coupling processing technique,
That is anaerobic membrane electricity biological treatment has many advantages, such as that cost of investment is few, floor space is small, easy to operate, improvement effect is notable.
Conductive film plays film retention and membrane electrode effect simultaneously：The organic matter in waste water is retained, its contact with anaerobe is extended
Time improves the treatment effeciency of organic matter under the conditions of low hydraulic detention time；The electroactive microorganism of Electro Sorb, quickly forms anode
Biomembrane optimizes self-conductive performance, strengthens effluent quality, improves methane production.Meanwhile the booster action of electrochemistry can be with
Change conductive membrane property, improve its permeance property, separating property and antifouling property, extends conductive film service life.Therefore, detest
Oxygen film electricity biological treatment can be realized simultaneously in the alleviation of membrane pollution of membrane bioreactor original position and shorter hydraulic detention time
The efficient removal of organic matter effectively releases application limit of the technique in terms of the low-intensity treatment of Organic Wastewater such as city domestic sewage
System.
The present invention will be further described with example below in conjunction with the accompanying drawings：
As shown in Figure 1, the anaerobic membrane electricity biological treatment device of this low-intensity organic wastewater, has following technology special
Sign：Upflow anaerobic sludge blanket reactor equipped with insulating layer ii-39 is placed on pedestal 44, its underpart be equipped with water distributor 43,
Grain sludge area 14 and suspended sludge area 15 are set to the upflow anaerobic sludge blanket reactor inner cavity from top to bottom.Intake pump
Intake pool 46 is inserted into 9 one end via pipe vi-45, and the other end is via the bottom of pipe i-8, valve i-10 and the water distributor 43
Connection.At least a pair of of carbon electrode 40 is equipped in granule sludge area 14, the titanium silk i-12 connections carbon electrode 40 simultaneously passes through institute
State the connecting line of the through-hole i-13 and 3 connection jaws iii-6 of electrochemical workstation of upflow anaerobic sludge blanket reactor lower part side
Iii-7 is connected to tie point i-11.Pipe v-41,14 other side of valve v-42 connection granule sludges area lower part.Pressure gauge ii-36
It is connected to 15 top of suspended sludge area via valve iv-35 and pipe iv-38.The middle part of upflow anaerobic sludge blanket reactor is equipped with
Membrane bioreactor 32.32 bosom of membrane bioreactor is equipped with conductive film 34, and washer 16 is separately positioned on the conduction
The both sides up and down of film 34.Titanium silk ii-18 is connected with 34 surface of conductive film and passes through connecing for through-hole ii-19 and electrochemical workstation 3
The connecting line ii-2 of line mouth i-4 is connected to tie point ii-17.On upflow anaerobic sludge blanket reactor equipped with insulating layer i-20
Portion is three-phase separation area 22, and three phase separator 21 and reference electrode 25 are individually fixed in the upper of upflow anaerobic sludge blanket reactor
Lid.21 upper port of three phase separator setting collection gas port 26；The top of reference electrode 25 be connected with titanium silk iii-24 and with electrification
The connecting line i-1 for learning 3 connection jaws i-5 of work station is connected to tie point iii-23；Pressure gauge i-29 is through valve iii-33 and pipe
Iii-31 is connected to the lower part of three-phase separation area 22.Water outlet of the sides valve ii-28 through pipe ii-27 Yu 22 top of three-phase separation area
Mouth is connected, and the other side is discharged into discharge bay 47 through pipe vii-48.
This anaerobic membrane electricity biological treatment carried out to low-intensity organic wastewater using above-mentioned apparatus includes following tool
Body operational sequence：
In draught cupboard, 10mL concentrated nitric acids are first slowly added into 250mL beakers, then the dense sulphur of 30mL is slowly added to along wall of cup
Acid, it is stirring while adding, prepare 40mL nitration mixture (volume ratios 1:3) spare.
Carbon nanotube 0.5~1.5g that particle size range is 40-60nm is slowly added into above-mentioned nitration mixture, it is stirring while adding,
Until carbon nanotube is completely dissolved in nitration mixture；Preferably, weighing 1g carbon nanotubes is dissolved in nitration mixture.
The above-mentioned solution that is thoroughly mixed is poured slowly into 250mL round-bottomed flasks, after being sealed with preservative film, heating is placed in and packs into
Row agitating and heating, heating time are 20~30min, and temperature is controlled at 60~80 DEG C；Preferably, 80 DEG C of constant temperature stirrings of selection add
Hot 30min experiment conditions, to realize the complete acidification of carbon nanotube.After stopping heating, round-bottomed flask, air cooling are taken out.
Using 1000mL beakers, built-in 800mL deionized waters.Mixed solution in round-bottomed flask after cooling is slowly fallen
Enter wherein, it is stirring while adding, it is used in combination deionized water to rinse round-bottomed flask repeatedly, flushing liquor is poured into beaker, until in beaker
Liquid is to 1000mL.Beaker is sealed with preservative film, stands 10~15h.Preferably, selection stands 15h, can obviously observe interior
Portion's mixed liquor layering.
The supernatant liquor of layering mixed liquor is outwelled after will be static, and by the way that method is filtered by vacuum, surplus solution is filtered
On 0.45 μm of moisture film, deionized water is used in combination to rinse beaker bottom repeatedly, continues to filter flushing liquor, until beaker bottom is without remnants
Black solid.
The carbon nanotube after the water film surface acidification for filtering and completing is scraped with spoon, glass plate surface is placed in, at 80 DEG C
Under the conditions of carry out drying drying.It after the completion of drying, places it in beaker, stores at ambient temperature spare.
The carbon nanotube that 0.03~0.06g is dried for standby is taken, is added in 100mL dimethylformamides, it is stirring while adding, then
Ultrasonic 2h, makes it completely dissolved, and conducting membrane material preparation solution is made.Again by the method for vacuum filtration, by the system of 10~30mL
Standby liquid is loaded on the glass fibre membrane of diameter 40mm.Preferably, the process uses 0.05g carbon nanotubes/(100mL diformazans
Base formamide solution) conducting membrane material preparation solution, vacuum loading is carried out with 20mL preparation solutions/film.
Film after load preparation solution is placed in progress 2~2.5h of high temperature sintering in 250~300 DEG C of stove, is prepared a diameter of
The carbon nanotube of 40mm-glass fibre conductive film；Preferably, temperature programming condition setting is：Heating rate is 5 DEG C/min,
Sintering temperature is 300 DEG C, sintering time 2h.
Anaerobic biological treatment apparatus is started using the digested sludge for being derived from anaerobic sludge fermentation tank, makes granule sludge area
Sludge concentration reaches 10~20g/L.
It takes the conductive film 34 for preparing and completing to be placed in membrane bioreactor 32, surface is connected with titanium silk ii-18, by logical
Hole ii-19 is connected to outside device.Upflow anaerobic sludge blanket reactor lower part is placed in using conductor material carbon-point 40, surface with
Titanium silk i-12 is connected, and is connected to outside device by through-hole i-13；Optimum condition：In order to realize good electric conductivity, choose
The carbon-point 40 of four diameter 10mm, long 35mm are connected by titanium silk i-12 between every carbon-point 40.
Electrochemical workstation 3 is opened, the titanium silk iii-24 and connecting line i-1 being connected with reference electrode 25 are connected to tie point
Iii-23, the titanium silk ii-18 and connecting line ii-2 being connected with conductive film 34 are connected to tie point ii-17, are connected with carbon-point 40
Titanium silk i-12 and connecting line iii-7 are connected to tie point i-11.Setting cathode potential is 0V, changes anode potential, two electricity of control
Voltage across poles is within the scope of 0.8~1.2V；Preferably, control voltage is 1.0V.
Open intake pump 9 and valve i-10, low-intensity organic wastewater from intake pool 46 successively via pipe vi-45, pipe i-8,
Water distributor 43, into upflow anaerobic sludge blanket reactor lower part granule sludge area 14.Hydraulic detention time is controlled in 4~8h,
Optimal water power standing time is 6h；At 25~30 DEG C, optimum temperature is 30 DEG C for temperature control.
Valve iv-35 is opened, the organic wastewater before the retention of conductive film 34 is obtained via pipe iv-38 surge table ii-36
Number pressure before film；Valve iii-33 is opened, by the processed waste water of conductive film 34 via pipe iii-31 surge table i-29,
Obtain number pressure after film.The difference of the two, as transmembrane pressure.
Pass through conduction under hydraulic blow effect by certain anaerobic membrane biosystem treated organic wastewater before conductive film 34
Film layer, into upflow anaerobic sludge blanket reactor top, three-phase separation area 22 complete water, qi leel from.Open valve ii-
28, water outlet up to standard is stored in through pipe ii-27, valve ii-28, pipe vii-48 bleeders in discharge bay 47；The gas of generation is through three
21 discharger of phase separator is effectively collected in collection gas port 26.
Liquid volume in discharge bay 47 is measured every 12~15h.As preferred：Every 15h, 47 liquid bulk of discharge bay is measured
Product.
As shown in Fig. 2, with the change of hydraulic detention time, compared with common Anaerobic treatment technique, using described
The anaerobic membrane electricity biological treatment of low-intensity organic wastewater, methane production maintain higher level always.In hydraulic retention
Between when being 6h, the methane production of anaerobic membrane electricity biological treatment improve significantly, about common anaerobic bio-treated work
4 times of skill.
As shown in figure 3, with the change of hydraulic detention time, compared with common Anaerobic treatment technique, using described
The anaerobic membrane electricity biological treatment of low-intensity organic wastewater, the concentration for being discharged COD maintain more low-level always
(being less than 35mg/L).When hydraulic detention time is 6h, the water outlet COD of anaerobic membrane electricity biological treatment occurs most
Low value, about 23mg/L.
As shown in figure 4, with the change of hydraulic detention time, compared with common Anaerobic treatment technique, using described
The anaerobic membrane electricity biological treatment of low-intensity organic wastewater, delivery turbidity maintain more low-level (being less than 22NTU) always.
When hydraulic detention time is 6h, there is minimum, about 15NTU in the delivery turbidity of anaerobic membrane electricity biological treatment.
Claims (4)
1. a kind of anaerobic membrane electricity biological treatment device of low-intensity organic wastewater, it is characterised in that：Equipped with insulating layer ii
(39) upflow anaerobic sludge blanket reactor is placed on pedestal (44), and its underpart is equipped with water distributor (43), granule sludge area
(14) and suspended sludge area (15) are set to the upflow anaerobic sludge blanket reactor inner cavity from bottom to top；Intake pump (9)
One end via pipe vi (45) be inserted into intake pool (46) and the other end via pipe i (8), valve i (10) and the water distributor
(43) bottom connection；At least a pair of of carbon electrode (40) is equipped in the granule sludge area (14)；Described in titanium silk i (12) connections
Carbon electrode (40) and the through-hole i (13) and electrochemical workstation for passing through upflow anaerobic sludge blanket reactor lower part side
(3) the connecting line iii (7) of connection jaws iii (6) is connected to tie point i (11)；Pipe v (41), valve v (42) the connection particle
The lower part of sludge area (14) other side；Pressure gauge ii (36) is connected to the suspended sludge via valve iv (35) and pipe iv (38)
Area (15) top；The middle part of the upflow anaerobic sludge blanket reactor is equipped with membrane bioreactor (32)；The membrane biological reaction
Device (32) bosom is equipped with conductive film (34), and washer (16) is separately positioned on the both sides up and down of the conductive film (34)；Titanium silk
Ii (18) is connected with the conductive film (34) surface and passes through through-hole ii (19) and the connection jaws i's (4) of electrochemical workstation (3)
Connecting line ii (2) is connected to tie point ii (17)；The upflow anaerobic sludge blanket reactor top equipped with insulating layer i (20)
For three-phase separation area (22), the three phase separator (21) and reference electrode (25) are individually fixed in the upflow anaerobic sludge
The upper cover of bed reactor；Three phase separator (21) the upper port setting collection gas port (26)；The reference electrode (25) it is upper
Portion is connected with titanium silk iii (24) and is connected to tie point iii with the connecting line i (1) of electrochemical workstation (3) connection jaws i (5)
(23)；Pressure gauge i (29) is connected to the lower part of the three-phase separation area (22) through valve iii (33) and pipe iii (31)；Valve ii
(28) side is connected through pipe ii (27) with the water outlet on the three-phase separation area (22) top and the other side is discharged into through pipe vii (48)
Discharge bay (47).
2. a kind of anaerobic membrane electricity biological treatment device of low-intensity organic wastewater according to claim 1, feature
It is：The carbon electrode (40) is to electrode, and quantity is 2 pairs.
3. a kind of anaerobic membrane electricity biological treatment device of low-intensity organic wastewater according to claim 1, feature
It is：The conductive film (34) is working electrode.
4. it is a kind of using device described in claim 1 to the anaerobic membrane electricity biological treatment of low-intensity organic wastewater include with
Lower process：
1) in draught cupboard, 10mL concentrated nitric acids are first slowly added into 250mL beakers, then the dense sulphur of 30mL is slowly added to along wall of cup
Acid, it is stirring while adding, prepare 40mL nitration mixture (volume ratios 1:3) spare；
2) carbon nanotube 0.5~1.5g that particle size range is 40-60nm is slowly added into above-mentioned nitration mixture, it is stirring while adding, directly
It is completely dissolved in nitration mixture to carbon nanotube；Preferably, weighing 1g carbon nanotubes is dissolved in nitration mixture；
3) the above-mentioned solution that is thoroughly mixed is poured slowly into 250mL round-bottomed flasks, after being sealed with preservative film, is placed in heating mantle progress
Agitating and heating, heating time are 20~30min, and temperature is controlled at 60~80 DEG C；Preferably, 80 DEG C of constant temperature agitating and heatings of selection
30min experiment conditions, to realize the complete acidification of carbon nanotube；After stopping heating, round-bottomed flask, air cooling are taken out；
4) 1000mL beakers, built-in 800mL deionized waters are used；Mixed solution in round-bottomed flask after cooling is poured slowly into
Wherein, stirring while adding, it is used in combination deionized water to rinse round-bottomed flask repeatedly, flushing liquor is poured into beaker, until liquid in beaker
Body is to 1000mL；Beaker is sealed with preservative film, stands 10~15h；Preferably, selection stands 15h, inside can be obviously observed
Mixed liquor is layered；
5) supernatant liquor of layering mixed liquor is outwelled after will be static, and by the way that method is filtered by vacuum, surplus solution is filtered in 0.45 μ
On m moisture films, deionized water is used in combination to rinse beaker bottom repeatedly, continues to filter flushing liquor, until beaker bottom does not have remaining black
Solid；
6) carbon nanotube after the water film surface acidification for filtering and completing is scraped with spoon, glass plate surface is placed in, in 80 DEG C of items
Drying drying is carried out under part；It after the completion of drying, places it in beaker, stores at ambient temperature spare；
7) carbon nanotube for taking 0.03~0.06g to be dried for standby is added in 100mL dimethylformamides, stirring while adding, then surpasses
Sound 2h, makes it completely dissolved, and conducting membrane material preparation solution is made；Again by the method for vacuum filtration, by the preparation of 10~30mL
Liquid is loaded on the glass fibre membrane of diameter 40mm；Preferably, the process uses 0.05g carbon nanotubes/(100mL dimethyl
Formamide solution) conducting membrane material preparation solution, vacuum loading is carried out with 20mL preparation solutions/film；
8) film after load preparation solution is placed in progress 2~2.5h of high temperature sintering in 250~300 DEG C of stove, prepared a diameter of
The carbon nanotube of 40mm-glass fibre conductive film；Preferably, temperature programming condition setting is：Heating rate is 5 DEG C/min,
Sintering temperature is 300 DEG C, sintering time 2h；
9) anaerobic biological treatment apparatus is started using the digested sludge for being derived from anaerobic sludge fermentation tank, makes the dirt in granule sludge area
Mud concentration reaches 10~20g/L；
10) it takes the conductive film (34) for preparing and completing to be placed in membrane bioreactor (32), surface is connected with titanium silk ii (18), leads to
Through-hole ii (19) is crossed to be connected to outside device；It is placed under upflow anaerobic sludge blanket reactor using conductor material carbon-point (40)
Portion, surface are connected with titanium silk i (12), are connected to outside device by through-hole i (13)；Optimum condition：In order to realize good lead
Electrical property chooses the carbon-point (40) of four diameter 10mm, long 35mm, is connected by titanium silk i (12) between every carbon-point (40)；
11) electrochemical workstation (3) is opened, the titanium silk iii (24) and connecting line i (1) being connected with reference electrode (25) are connected to
Tie point iii (23), the titanium silk ii (18) and connecting line ii (2) being connected with conductive film (34) are connected to tie point ii (17), with
Carbon-point (40) connected titanium silk i (12) and connecting line iii (7) is connected to tie point i (11)；Setting cathode potential is 0V, is changed
Anode potential, two inter-electrode voltages of control are within the scope of 0.8~1.2V；Preferably, control voltage is 1.0V；
12) intake pump (9) and valve i (10) are opened, low-intensity organic wastewater is from intake pool (46) successively via pipe vi (45), pipe
I (8), water distributor (43), into upflow anaerobic sludge blanket reactor lower part granule sludge area (14)；Hydraulic detention time controls
In 4~8h, optimal water power standing time 6h；At 25~30 DEG C, optimum temperature is 30 DEG C for temperature control；
13) open valve iv (35), the organic wastewater before conductive film (34) retention via pipe iv (38) surge table ii (36),
Obtain number pressure before film；Valve iii (33) is opened, by the processed waste water of conductive film (34) via pipe iii (31) percussive pressure
Power table i (29), obtains number pressure after film；The difference of the two, as transmembrane pressure；
14) by certain anaerobic membrane biosystem, treated that organic wastewater passes through conduction under hydraulic blow effect before conductive film (34)
Film layer, into upflow anaerobic sludge blanket reactor top, three-phase separation area (22) complete water, qi leel from；Open valve ii
(28), water outlet up to standard is stored in through pipe ii (27), valve ii (28), pipe vii (48) bleeder in discharge bay (47)；It generates
Gas is effectively collected through three phase separator (21) discharger in collection gas port (26)；
15) discharge bay (47) interior liquid volume is measured every 12~15h；As preferred：Every 15h, discharge bay (47) liquid is measured
Body volume.
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