CN107032479A - The method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water - Google Patents
The method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water Download PDFInfo
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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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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Abstract
The present invention relates to the method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water, this method includes inoculating active anaerobic sludge, active aerobic sludge, after inoculation membrane formation, Ciprofloxacin waste water pass through using lytag be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism microelectrolysis processing, during processing simultaneously impressed DC voltage；Obtained coupling processing waste water passes through using sludge ceramsite as filler, and clarification and effluent is obtained after carrying out Aerobic Process for Treatment, processing under the conditions of impressed DC voltage.The processing method of the present invention is by bioelectrochemical system and light electrolysis system integration one, by applied voltage, removes Pollutants in Wastewater, and the coupled system startup time is short, and operation operation is easy；Clarification of water, while can efficiently remove water outlet after COD, TN and TP, processing will not produce a large amount of black muds, can be gone out with efficient degradation high concentration Ciprofloxacin, not result in secondary pollution, treatment effeciency is high.
Description
Technical field
The present invention relates to a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration Ciprofloxacin waste water
Method, belong to technical field of waste water processing.
Background technology
Ciprofloxacin belongs to third generation carbostyril antibiotic, because it has good restraining and sterilizing bacteria effect, has a broad antifungal spectrum, price
Cheap the features such as, it is widely used in clinical, animal husbandry and culture fishery, as most widely used in current QNS
General kind.Ciprofloxacin pharmacy waste water belongs to high concentration hard-degraded organic waste water, and waste water COD is up to more than 10000mg/L, contains
Nitrogen reaches the Ciprofloxacin that higher concentration is usually contained in 1000mg/L, and waste water, and in some produced in production process
Between product, such as toluene, aminate, cyclopropyl carboxylic acid cause wastewater biodegradability poor, it is difficult to directly to carry out biochemical treatment.And
And, with sharply increasing for Ciprofloxacin yield, the pharmacy waste water produced in its production process is consequently increased, thus how to be had
The Ciprofloxacin pharmacy waste water that largely produces of effect processing, have become one it is very severe the problem of.Due to Ciprofloxacin very
Difficult degradation, Technology development and technique traditional at present can not thoroughly remove the antibiotic, Yi Zao such as the Ciprofloxacin in waste water
Into receiving water body and excess sludge receive the antibiotic such as ground contamination, and Ciprofloxacin be present in environment water can be to the ecosystem
Cause great potential threat.Therefore, a kind of new processing work for being directed to high concentration Ciprofloxacin pharmacy waste water is worked out
Skill has important practical significance.
At present, the domestic processing to Ciprofloxacin pharmacy waste water is still in the exploratory stage.Domestic Ciprofloxacin antibiotic
Wastewater treatment is mainly using the multilevel processing technology of pretreatment plus subsequent biochemical processing.But still do not solve waste water in contain it is big
The problem of measuring hardly degraded organic substance, causes water outlet to be difficult to reach discharge standard, and it is exceeded to be mainly manifested in COD, N content and colourity,
And water outlet remains to detect the Ciprofloxacin presence of higher concentration.
Chinese patent literature CN104445814A (application numbers：201410664259.6) disclose a kind of processing Tetracyclines
The technique and device of antibiotic waste water.The technique includes iron-carbon micro-electrolysis pretreatment and aerobic/anaerobic biological treatment, wherein iron carbon
Light electrolysis is using iron carbon haydite as micro-electrolysis material, and aerobic/anaerobic biological treatment is then respectively with lytag and sludge ceramsite
It is used as filler.Anaerobism is combined and carried out in a reactor by the technique with Aerobic biological process, simplifies technological process, is reduced
Capital cost；The organic principle in tetracycline wastewater, such as COD, total phosphorus and total nitrogen can be effectively removed, and Tetracyclines is divided greatly
Sub- bacteriostatic antibiotic has good degradation effect.Found in During Process of Long-term Operation, the pretreatment water outlet upon mediation of iron carbon haydite
A large amount of black muds can be produced after pH, are not only difficult to handle, secondary pollution is produced, and cause water outlet muddy, to subsequent biological treatment
Have a negative impact；Iron carbon haydite is made of iron powder and carbon dust, is added processing cost, is also easy to produce waste.It is simultaneously long-term to transport
It has also been found that detesting/aerobic combination biofilter fluctuation of service in row, capacity of resisting impact load is poor, to external world environment and service condition
Change is sensitive, and limited to high concentration COD removal ability, and this is probably because detesting/aerobic microbiological one reactor of processing
Interior, one side packed height not enough, causes treatment effect undesirable, is on the other hand also easy to produce and influences each other, be unfavorable for the two each
From biocoene it is stable.
The content of the invention
In view of the shortcomings of the prior art, the present invention is provided at a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying
The method for managing high concentration Ciprofloxacin waste water, method of the invention can be with efficient degradation high concentration Ciprofloxacin, while can be efficiently
COD TN and TP are removed, water outlet will not produce a large amount of black muds after processing, go out clarification of water, not result in secondary pollution, of the invention
Device is stable in longtime running, is conducive to biocenological fixation, and capacity of resisting impact load is strong.
Technical scheme is as follows：
The method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water, bag
Include step as follows：
(1) the reactor start-up stage：In bioelectrochemistry anaerobism/microelectrolysis processing device and aerobic treatment device respectively
Inoculating active anaerobic sludge, active aerobic sludge, intake 4 days at low flow rates, microorganism is attached to haydite surface and form one
The uniform biomembrane of layer, biofilm thickness is 1-2mm；
(2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with flyash ceramic
Grain be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing, processing
When simultaneously additional some strength DC voltage；The volume ratio that lytag is mixed with iron aluminium carbon haydite is (2~5):1, electricity
Voltage-controlled system is 0.1~0.6L/h, hydraulic detention time 6-10h in 0.5-1.4V, influent waste water speed, after processing, is coupled
Handle waste water；
(3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing with sludge by being made pottery
Grain is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 0.5-1.4V, flow rate 0.1~
0.6L/h, hydraulic detention time 6-10h, gas-water ratio (14~18):1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is
800-1000kg/m3, 500~600kg/m of bulk density3, clarification and effluent is obtained after processing.
It is currently preferred, it is aerobic using applied voltage in bioelectrochemistry anaerobism/integral process step of light electrolysis blending
Water is flowed back after processing, and reflux ratio is (2-6)：1, filler is backwashed, backwashing period is 5-7 days.
Currently preferred, step (1) water inlet flow velocity is 0.1-0.3L/h.
Currently preferred, described iron aluminium carbon haydite particle diameter is 0.5-1cm, and grain density is 1250-1500kg/m3,
3~8kg/m of bulk density3；Described lytag particle diameter is 2-3cm, and grain density is 750-850kg/m3, bulk density
400~500kg/m3, 80~120cm of packed height of compound.
Currently preferred, the volume ratio that lytag is mixed with iron aluminium carbon haydite is (4~5):1.
Currently preferred, described iron aluminum-carbon ternary light electrolysis haydite is using Fenton iron cement, aluminium powder, activated carbon as original
Material, Fenton iron cement, aluminium powder, the mass ratio of activated carbon are：(1~5)：(1~3)：(0.1~2), is added after binding agent and by spray
Spill into globule and carry out granulation balling-up, then dried raw material ball is placed in anaerobic at 600~650 DEG C of temperature and sinters 1~2h, obtains
Anode and cathode Integral iron aluminum-carbon ternary light electrolysis haydite.
It is further preferred that the mass ratio of Fenton iron cement, aluminium powder, activated carbon is：1：1：2.
Currently preferred, described binding agent is polyvinyl alcohol.
Described is to be heated after polyvinyl alcohol, sodium carboxymethylcellulose and nickel sulfate hexahydrate are mixed after water dilution into globule
In mixed solution, mixed solution, the mass concentration of polyvinyl alcohol is 3~6wt%, the mass concentration 2 of sodium carboxymethylcellulose~
4wt%, nickel sulfate hexahydrate mass concentration is 1~2wt%.
Currently preferred, content of organics is 40-50% in described Fenton iron cement, and iron content is 20-30%.
Currently preferred, binding agent, the mass ratio into globule and Fenton iron cement are：(1~5)：(0.1~1)：(1~
5)。
Fenton iron cement is the iron containing sludge produced during Fenton oxidation process operation, due to Fenton technology application time not
It is long, lack corresponding sludge treatment experience and prototyping method, the present invention regard Fenton iron cement as iron aluminum-carbon ternary light electrolysis haydite
Source of iron, not only reduces engineering cost, and by the treatment of wastes with processes of wastes against one another, a feasibility is provided for the processing disposal of Fenton iron cement
Path.
Currently preferred, Ciprofloxacin influent waste water pH is 6-8, and the wastewater pH after step (2) processing is 4-5,
Wastewater pH after step (3) processing is 6-7.
It is currently preferred, step (2), applied voltage control is in 0.8-1.2V, and influent waste water speed is 0.4~0.6L/
H, hydraulic detention time 8-10h.
It is currently preferred, step (3), applied voltage control is in 1.0-1.4V, and influent waste water speed is 0.2~0.4L/
H, hydraulic detention time 8-10h.
Using the method for the present invention, Ciprofloxacin Concentration 100-165mg/L before high concentration Ciprofloxacin wastewater treatment, processing
Concentration stabilization is in 6mg/L or so afterwards, and Ciprofloxacin clearance reaches 96%, while before processing COD concentration 6500-6700mg/L,
Water outlet COD is stable in 134mg/L, before processing ammonia nitrogen concentration 300-350mg/L after processing, and ammonia nitrogen concentration is stable in 7mg/ after processing
L。
Integral processing method is blended by bioelectrochemical system and light electrolysis in the bioelectrochemistry anaerobism of the present invention/light electrolysis
On the one hand system integration one, can directly remove Pollutants in Wastewater by applied voltage, on the other hand can also strengthen micro-
Be electrolysed treatment effect, promote anaerobe haydite surface growth and attachment, and then strengthen to Ciprofloxacin, COD, TN,
NH4- N and TP removal.First, bioelectrochemical system is the body of microorganism, reaction substrate and electrode triple interaction
System.Microorganism is typically attached on electrode, by with the direct or indirect electron transmission of electrode, by solution and electrode seal phase
Even.Microorganism on anode produces electronics and passes to anode by carbohydrate oxidation or sulfide；Negative electrode then utilizes sky
Gas, proton or other organic matters consume the electronics passed over from anode, so as to be maintained whole system as electron acceptor
Internal oxidition reduction reaction is continuously carried out.Secondly, control external dc electric current can promote bacterium thin in suitable intensity
Born of the same parents breed, total protein content in increase bacterial cell；The activity of bacterial cell ATP enzyme can be strengthened；Improve to a certain degree thin
Intracellular growth ability and metaboilic level.Electrochemical conditions have obvious stimulation to microorganism growth metabolism process, to bacterium
Electrode reaction product H2 and active H atom in applying direct current stimulating course can activate or strengthen the activity of ATP enzyme etc., right
There is good effect in the bioactivity reaction and raising microorganism growth metabolism vigor for promoting enzyme.It is additional certain in anaerobic system
Electric field has the increase of certain invigoration effect, mainly electric field to iron aluminium carbon micro-electrolysis, and the redox reaction of electrode is added
The degraded of organic matter.In this system, electrochemical reaction can reduction of the reinforced anaerobic microorganism to nitrate nitrogen, traditional is anti-
Nitrification processing process is under anoxic or anaerobic condition, nitrate nitrogen to be eventually converted into nitrogen using heterotroph denitrifying bacterium and reached
To the purpose of denitrogenation of waste water, and the hydrogen that electrical field stimulation is produced can as denitrifying bacteria electron donor, promote reduction reaction
Progress, so as to improve the reducing activity of microorganism.Iron-carbon micro-electrolysis process can produce substantial amounts of Fe simultaneously2+、Fe3+, and
Molysite and ferrous salt are current most widely used coagulant again, for removing substantial amounts of P elements in waste water, play chemistry mixed
Solidifying effect, therefore it has been greatly facilitated in the case of not additional chemical agent TP removal.Anaerobe processing then mainly exists
Worked on COD removals and denitrification, while the production acetic acid stage in anaerobic bio-treated can cause reaction system pH to drop to
5.0 or so, sour environment improves the treatment effeciency of iron aluminium carbon micro-electrolysis again just, therefore the method for the present invention can efficiently drop
High concentration Ciprofloxacin is solved, while can efficiently remove water outlet after COD, TN and TP, processing will not produce a large amount of black muds, water outlet is clear
Clearly, secondary pollution is not resulted in, treatment effeciency is high.
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles the device of high concentration Ciprofloxacin waste water, bag
Include the bioelectrochemistry anaerobism/microelectrolysis processing device and aerobic treatment device being connected, described bioelectrochemistry anaerobism/micro-
Electrolytic processing apparatus includes filling in bioelectrochemistry anaerobism/micro-electrolysis stuffing area, bioelectrochemistry anaerobism/micro-electrolysis stuffing area
The compound of lytag and iron aluminum-carbon ternary light electrolysis haydite, is inserted in bioelectrochemistry anaerobism/micro-electrolysis stuffing area
There are negative electrode and anode, negative electrode and anode external direct current power supply, form electro-chemical systems；Bioelectrochemistry anaerobism/micro-electrolysis stuffing
Area lower end is provided with filter plate, and the bottom of bioelectrochemistry anaerobism/microelectrolysis processing device passes through adpting flange and water inlet buffering area
It is fixedly connected, water inlet buffering area is connected with water inlet pipe, is provided with water inlet pipe at intake pump, bioelectrochemistry anaerobism/light electrolysis
The top of reason device, which is provided with top cover, top cover, is provided with gas outlet, and gas outlet is connected with gas storage device, bioelectrochemistry
On the side wall of anaerobism/microelectrolysis processing device and positioned at being provided with delivery port between top cover and packing area；
Described aerobic treatment device includes filling sludge ceramsite in aerobic packing area, aerobic packing area, in aerobic filler
Negative electrode and anode, negative electrode and anode external direct current power supply are fitted with area, electro-chemical systems are formed；Aerobic packing area lower end is set
Have and aeration plate is provided with filter plate, filter plate, aerobic treatment device bottom is fixedly connected by flange with aerobic water inlet buffering area,
Recycling effluent mouthful and aerobic delivery port are provided with the side wall of aerobic packing area；Bioelectrochemistry anaerobism/microelectrolysis processing device
Delivery port and the aerobic water inlet buffering area of aerobic treatment device connected by connecting tube, connecting tube is provided with peristaltic pump.
Currently preferred, the recycling effluent mouthful of aerobic treatment device passes through return duct and bioelectrochemistry anaerobism/micro- electricity
The water inlet buffering area connection of processing unit is solved, reflux pump is provided with return duct, by the effluent recycling of aerobic treatment device extremely
Handled in bioelectrochemistry anaerobism/microelectrolysis processing device.
Currently preferred, described negative electrode, anode are tubular structure, and negative electrode, anode use carbon fibre material.
Bioelectrochemistry anaerobism/microelectrolysis processing device of the present invention is compounded with bioelectrochemical system, that is, passes through electrolysis
Removal effect is directly played in effect to pollutant, also can promote the metabolism of aerobic microbiological simultaneously.Aerobic treatment device
Return-flow system is circumscribed with, water outlet is back to anaerobic reactor by certain Billy, further to remove nitrogen, phosphorus and Ciprofloxacin.
Bioelectrochemistry anaerobism/microelectrolysis processing device of the present invention designs heat-insulation layer with aerobic treatment device outer layer, fills out
Filled with insulation material, temperature of reaction system is ensured during to low temperature in the winter time.
The present invention without specified otherwise outside, raw materials used and equipment is prior art.
Advantages of the present invention is as follows：
1st, processing method of the invention is by bioelectrochemical system and light electrolysis system integration one, by applied voltage,
Pollutants in Wastewater is removed, the coupled system startup time is short, and operation operation is easy；Can with efficient degradation high concentration Ciprofloxacin,
Can efficiently remove water outlet after COD, TN and TP, processing will not produce a large amount of black muds simultaneously, go out clarification of water, do not result in secondary dirt
Dye, treatment effeciency is high.
2nd, method of the invention is high to high concentration Ciprofloxacin waste water treatment efficiency, and COD, TN, TP and Ciprofloxacin are removed
Rate respectively reaches 98%, 85%, 90% and 96%, thus can accomplish the simultaneous removing of carbon nitrogen phosphorus and Ciprofloxacin.
3rd, device coupled system of the invention is stable, anti-organic loading, and it is strong that Ciprofloxacin meets ability；Coupled system
The treatment of wastes with processes of wastes against one another, processing cost is low, and centre does not produce secondary pollution；Coupled system reduced investment, is conducive to wide popularization and application.
Brief description of the drawings
Fig. 1 handles high concentration Ciprofloxacin waste water for bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying of the present invention
Apparatus structure schematic diagram；
1-1,1-2, support；2-1,2-2, ring flange；3-1,3-2, aeration plate；4-1,4-2, filter plate；5th, bioelectrochemistry
Anaerobism/micro-electrolysis stuffing area；6th, aerobic packing area, 7,9 delivery ports；8th, water inlet, 10, aerobic water inlets, 11-1, recycling effluent
Mouthful, 11-2, outputted aerobic water mouthful, 12, bioelectrochemistry anaerobism/microelectrolysis processing device side wall, 13, aerobic treatment device side wall,
14th, caisson, 15, water inlet buffering area, 17, compound；16-1,16-2,16-3 peristaltic pump, 18-1,18-2 top cover, 19-1,
19-2 anodes, 20-1,20-2 negative electrode.
Embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Sludge ceramsite is prepared with reference to Chinese patent document CN101638312A in embodiment, and lytag is with reference to dirty
Mud haydite preparation method is prepared from, and reactor material is made of polytetrafluoroethylene (PTFE).
Active anaerobic sludge is derived from Jinan municipal sewage plant anaerobic zone, and active aerobic sludge is derived from Jinan municipal sewage
Treatment plant aerobic zone.
Embodiment 1
The method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water, bag
Include step as follows：
(1) the reactor start-up stage：In bioelectrochemistry anaerobism/microelectrolysis processing device and aerobic treatment device respectively
Inoculating active anaerobic sludge, active aerobic sludge, at low flow rates (0.2L/h) thing be attached to haydite surface and form a layer thickness
For 1mm biomembrane；
(2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with flyash ceramic
Grain be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing, processing
When simultaneously additional some strength DC voltage；The volume ratio that lytag is mixed with iron aluminium carbon haydite is 2:1, voltage control
In 0.6V, influent waste water speed is 1.0L/h, hydraulic detention time 6h, after processing, obtains coupling processing waste water；Described iron aluminium
Carbon haydite particle diameter is 0.5-1cm, and grain density is 1250-1500kg/m3, 3~8kg/m of bulk density3；Described flyash ceramic
Grain particle diameter is 2-3cm, and grain density is 750-850kg/m3, 400~500kg/m of bulk density3, the packed height of compound
90cm, described iron aluminum-carbon ternary light electrolysis haydite be using Fenton iron cement, aluminium powder, activated carbon as raw material, Fenton iron cement, aluminium powder,
The mass ratio of activated carbon is：(1~5)：(1~3)：(0.1~2), adds after binding agent and is granulated by spraying into globule
Balling-up, then dried raw material ball be placed at 600~650 DEG C of temperature anaerobic and sinter 1~2h, obtained anode and cathode Integral iron
Aluminum-carbon ternary light electrolysis haydite.Described binding agent is polyvinyl alcohol.It is described into globule be polyvinyl alcohol, carboxymethyl cellulose
Mixed solution after sodium and nickel sulfate hexahydrate mixing after heating water dilution, in mixed solution, the mass concentration of polyvinyl alcohol for 3~
6wt%, 2~4wt% of mass concentration of sodium carboxymethylcellulose, nickel sulfate hexahydrate mass concentration are 1~2wt%.Described sweet smell
Content of organics is 40-50% in iron cement of pausing, and iron content is 20-30%.Binding agent, into globule and the quality of Fenton iron cement
Than for：(1~5)：(0.1~1)：(1~5).
(3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing with sludge by being made pottery
Grain is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 0.6V, flow rate 1.0L/h, waterpower
Residence time 6h, gas-water ratio 15:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, accumulate close
Spend 500~600kg/m3, clarification and effluent is obtained after processing.
The device of above-mentioned use, as shown in figure 1, including bioelectrochemistry anaerobism/microelectrolysis processing device for being connected with
Aerobic treatment device, described bioelectrochemistry anaerobism/microelectrolysis processing device includes bioelectrochemistry anaerobism/micro-electrolysis stuffing
The compound of lytag and iron aluminum-carbon ternary light electrolysis haydite is filled in area 5, bioelectrochemistry anaerobism/micro-electrolysis stuffing area
17, negative electrode 20-1 and anode 19-1, negative electrode and the external direct current of anode are fitted with bioelectrochemistry anaerobism/micro-electrolysis stuffing area
Power supply, forms electro-chemical systems；Bioelectrochemistry anaerobism/micro-electrolysis stuffing area lower end is provided with filter plate 4-1, and bioelectrochemistry is detested
The bottom of oxygen/microelectrolysis processing device is fixedly connected by adpting flange 2-1 with water inlet buffering area 15-1, water inlet buffering area 15-1
It is connected with water inlet pipe, intake pump 16-1 is provided with water inlet pipe, the top of bioelectrochemistry anaerobism/microelectrolysis processing device is set
Have and gas outlet is provided with top cover 18-1, top cover, gas outlet is connected with gas storage device 14, bioelectrochemistry anaerobism/micro- electricity
Solve on the side wall of processing unit and be located at and delivery port 7,9 is provided between top cover and packing area；
Described aerobic treatment device includes filling sludge ceramsite in aerobic filler 6, aerobic packing area, in aerobic packing area
Negative electrode 20-2 and anode 19-2, negative electrode and anode external direct current power supply are inside fitted with, electro-chemical systems are formed；Under aerobic packing area
End, which is provided with filter plate 4-2, filter plate, is provided with aeration plate 3-1,3-2, and aerobic treatment device bottom passes through flange and aerobic water inlet
Slow area 15-2 is fixedly connected, and recycling effluent mouthful 11-1 and aerobic delivery port 11-2 is provided with the side wall of aerobic packing area；It is raw
The delivery port of thing electrochemistry anaerobism/microelectrolysis processing device and the aerobic water inlet buffering area of aerobic treatment device are connected by connecting tube
Connect, connecting tube is provided with peristaltic pump.The recycling effluent of aerobic treatment device mouthful 11-1 by return duct and bioelectrochemistry anaerobism/
The water inlet buffering area 15-1 connections of microelectrolysis processing device, are provided with reflux pump, by going out for aerobic treatment device on return duct
Water is back in bioelectrochemistry anaerobism/microelectrolysis processing device and handled.Described negative electrode, anode are tubular structure, cloudy
Pole, anode use carbon fibre material.
Embodiment 2
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration ring third described in be the same as Example 1 is husky
The method of star waste water, difference is：
Step (2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with fine coal
Grey haydite be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing,
While the DC voltage of additional some strength during processing；The volume ratio that lytag is mixed with iron aluminium carbon haydite is 3:1, voltage
Control is 0.9L/h, hydraulic detention time 8h in 0.7V, influent waste water speed, after processing, obtains coupling processing waste water；Described
Iron aluminium carbon haydite and lytag be the same as Example 1.
Step (3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing passes through with dirt
Mud haydite is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 0.7V, flow rate 0.9L/h,
Hydraulic detention time 8h, gas-water ratio 15:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, heap
500~600kg/m of product density3, clarification and effluent is obtained after processing.
Experimental result：Intake as synthetic wastewater, using glucose as carbon source, anaerobism, aerobic reactor water inlet carbon N/P ratio
Example is controlled 200 respectively:5:1 and 100:5:1；Anaerobic reactor influent COD 1000mg/L, aerobic reactor influent COD is
500mg/L；Intake using up-flow, continuum micromeehanics mode；Anaerobism, aerobic water inlet Ciprofloxacin are below 5mg/L；This stage returns
Streaming system is not run.Anaerobism, aerobic biofilter respectively through 30 days and 10 days, the two to COD, ammonia nitrogen clearance all
More than 80% is reached, this indicates two systems start completion, i.e. bioelectrochemistry-iron-carbon micro-electrolysis/anaerobism ceramic aggregate biological filter
The cell system startup time is only 30 days, and bioelectrochemistry-aerobic bio-ceramic filter system start-up time is only 10 days, the two
The startup time all greatly shortens than existing report result, and treatment effeciency is higher.
System normal operating phase：Normal operating phase, system water inlet uses synthetic wastewater, and anaerobic reactor water outlet is by entering
Water pump enters aerobic reactor；Now anaerobism, aerobic reactor water inlet flow control 6h between 0.5L/h, waterpower stopping time, aerobic
Biofilter gas-water ratio control is 15:1；System water inlet carbon N/P ratio control is 200:5:1, influent COD 1000mg/L, ring third are husky
Star 10mg/L；Applied voltage is 0.5V；Reflux ratio control is 5:1.
Embodiment 3
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration ring third described in be the same as Example 1 is husky
The method of star waste water, difference is：
Step (2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with fine coal
Grey haydite be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing,
While the DC voltage of additional some strength during processing；The volume ratio that lytag is mixed with iron aluminium carbon haydite is 4:1, voltage
Control is 0.8L/h, hydraulic detention time 10h in 0.8V, influent waste water speed, after processing, obtains coupling processing waste water；It is described
Iron aluminium carbon haydite and lytag be the same as Example 1.
Step (3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing passes through with dirt
Mud haydite is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 0.8V, flow rate 0.8L/h,
Hydraulic detention time 10h, gas-water ratio 15:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, heap
500~600kg/m of product density3, clarification and effluent is obtained after processing.
Experimental result：Intake as synthetic wastewater, using glucose as carbon source, anaerobism, aerobic reactor water inlet carbon N/P ratio
Example is controlled 200 respectively:5:1 and 100:5:1；Anaerobic reactor influent COD 1000mg/L, aerobic reactor influent COD is
500mg/L；Intake using up-flow, continuum micromeehanics mode；Anaerobism, aerobic water inlet Ciprofloxacin are below 5mg/L；This stage returns
Streaming system is not run.
The reactor operation phase：System water inlet uses synthetic wastewater, and anaerobic reactor water outlet is entered aerobic anti-by intake pump
Answer device；Now anaerobism, aerobic reactor water inlet flow control 6h between 0.5L/h, waterpower stopping time, aerobic biofilter gas-water ratio
Control is 15:1；System water inlet uses synthetic wastewater, and carbon N/P ratio is controlled 200:5:1, influent COD 2000mg/L, ring third are husky
Star 20mg/L；Applied voltage is 1.0V；Reflux ratio control is 5:1.
Embodiment 4：System start method is same as Example 1.Normal operating phase, anaerobism, aerobic reactor feed water flow
Speed control 6h between 0.5L/h, waterpower stopping time, aerobic biofilter gas-water ratio is controlled 15:1；System water inlet is useless using synthesis
Water, carbon N/P ratio is controlled 200:5:1, influent COD 4000mg/L, Ciprofloxacin 40mg/L；Applied voltage is 1.0v；Reflux ratio
Control as 2:1.
Embodiment 4
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration ring third described in be the same as Example 1 is husky
The method of star waste water, difference is：
Step (2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with fine coal
Grey haydite be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing,
While the DC voltage of additional some strength during processing；The volume ratio that lytag is mixed with iron aluminium carbon haydite is 5：1, voltage
Control is 0.6L/h, hydraulic detention time 10h in 0.9V, influent waste water speed, after processing, obtains coupling processing waste water；It is described
Iron aluminium carbon haydite and lytag be the same as Example 1.
Step (3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing passes through with dirt
Mud haydite is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 0.9V, flow rate 0.6L/h,
Hydraulic detention time 10h, gas-water ratio 10:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, heap
500~600kg/m of product density3, clarification and effluent is obtained after processing.System flowback is than control 5:1.
Embodiment 5
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration ring third described in be the same as Example 1 is husky
The method of star waste water, difference is：
Step (2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with fine coal
Grey haydite be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing,
While the DC voltage of additional some strength during processing；The volume ratio that lytag is mixed with iron aluminium carbon haydite is:4:1, electricity
Voltage-controlled system is 0.6L/h, hydraulic detention time 8h in 1.0V, influent waste water speed, after processing, obtains coupling processing waste water；It is described
Iron aluminium carbon haydite and lytag be the same as Example 1.
Step (3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing passes through with dirt
Mud haydite is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 1.0V, flow rate 0.6L/h,
Hydraulic detention time 8h, gas-water ratio 15:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, heap
500~600kg/m of product density3, clarification and effluent is obtained after processing.System flowback is than control 2:1.
Embodiment 6
A kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying processing high concentration ring third described in be the same as Example 1 is husky
The method of star waste water, difference is：
Step (2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water passes through with fine coal
Grey haydite be carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing,
While the DC voltage of additional some strength during processing；The volume ratio that lytag is mixed with iron aluminium carbon haydite is:4:1, electricity
Voltage-controlled system is 0.4L/h, hydraulic detention time 8h in 1.2V, influent waste water speed, after processing, obtains coupling processing waste water；It is described
Iron aluminium carbon haydite and lytag be the same as Example 1.
Step (3) applied voltage Aerobic Process for Treatment：Obtained coupling processing waste water after step (1) processing passes through with dirt
Mud haydite is filler, and Aerobic Process for Treatment is carried out under the conditions of impressed DC voltage, and voltage is controlled in 1.2V, flow rate 0.4L/h,
Hydraulic detention time 8h, gas-water ratio 15:1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-1000kg/m3, heap
500~600kg/m of product density3, clarification and effluent is obtained after processing.System flowback is than control 2:1.
Intake as synthetic wastewater, using glucose as carbon source, anaerobism, aerobic reactor water inlet carbon N∶P ratio are controlled respectively
200:5:1 and 100:5:1；Anaerobic reactor influent COD 1000mg/L, aerobic reactor influent COD is 500mg/L；Using
Up-flow, continuum micromeehanics mode are intake；Anaerobism, aerobic water inlet Ciprofloxacin are below 5mg/L；This stage return-flow system is not transported
OK.
Normal operating phase：System water inlet uses simulated wastewater, simulates the Ciprofloxacin pharmacy corporation water outlet of Jinan periphery,
Water quality index is as follows：COD is 6700mg/L, and BOD is 1840mg/L, ammonia nitrogen 350mg/L, total phosphorus 95mg/L, Ciprofloxacin
165mg/L, pH are 5.4.Anaerobism, aerobic treatment device packed height are 80cm, and water inlet flow velocity is 0.5L/h, hydraulic detention time
6h；Aerobic filter tank gas-water ratio 15:1, reflux ratio is 2:1；Backwashing period is 7 days.
Final system water outlet indices remove situation：COD clearances reach 98%, ammonia nitrogen removal frank 98%, total nitrogen
Clearance 85%, total tp removal rate 90%, Ciprofloxacin clearance 96%.Every water quality index reaches related industries discharge of wastewater
Standard.
Embodiment 1-6 see the table below shown in 1 to the result of Ciprofloxacin waste water：
Table 1
Contrast test：
Using experimental provision of the present invention have applied voltage with without applied voltage under the conditions of do contrast running experiment：
The simulation Ciprofloxacin pharmacy waste water water quality of human configuration is:COD is 6700mg/L, and BOD is 1840mg/L, ammonia nitrogen
2400mg/L, total phosphorus 95mg/L, Ciprofloxacin 165mg/L, pH are 5.4.Anaerobism, aerobic treatment device packed height are 80cm,
Water inlet flow velocity is 0.5L/h, hydraulic detention time 6h；Aerobic filter tank gas-water ratio 15:1, reflux ratio is 2:1；Backwashing period is 7
My god.Applied voltage is controlled in 0.5-1.4V.Longtime running result is found, under the conditions of without applied voltage, anaerobism/micro cell：
COD clearances 65%, Ciprofloxacin clearance 36%, total tp removal rate 30%；Aerobic biofilter：COD clearances 76%, ammonia
Nitrogen removal efficiency 82%, total tp removal rate 43%, Ciprofloxacin clearance 69%；By the overall clearance of the system that flows back：COD is gone
Except rate 75%, ammonia nitrogen removal frank 85%, nitrogen removal rate 72%, total tp removal rate 90%, Ciprofloxacin clearance 48%.For a long time
Operation result is found, under the conditions of specific making alive, anaerobism/micro cell：COD clearances 84%, Ciprofloxacin clearance
53%, total tp removal rate 42%；Aerobic biofilter：COD clearances 87%, ammonia nitrogen removal frank 86%, total tp removal rate 56%,
Ciprofloxacin clearance 81%；By the overall clearance of the system that flows back：COD clearances 91%, ammonia nitrogen removal frank 96%, total nitrogen
Clearance 87%, total tp removal rate 92%, Ciprofloxacin clearance 86%.It is possible thereby to find, additional specific voltage anaerobism/
To COD in light electrolysis filter tank, Ciprofloxacin has obvious facilitation on total phosphorus and nitrate removal, and to aerobic life
Thing filter tank COD, Ciprofloxacin, the removal of total phosphorus also has obvious increasing action.Every water quality index reaches related industries waste water
Discharge standard.Every water quality index reaches related industries wastewater discharge standard.
Claims (10)
1. the method that a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles high concentration Ciprofloxacin waste water, including
Step is as follows：
(1) the reactor start-up stage：It is inoculated with respectively in bioelectrochemistry anaerobism/microelectrolysis processing device with aerobic treatment device
Active anaerobic sludge, active aerobic sludge, intake 4 days at low flow rates, microorganism is attached to haydite surface and form one layer
Even biomembrane, biofilm thickness is 1-2mm；
(2) bioelectrochemistry anaerobism/light electrolysis blending one processing：High concentration Ciprofloxacin waste water pass through using lytag as
Carrier and using iron aluminum-carbon ternary light electrolysis haydite as the compound of filler in carry out anaerobic organism-microelectrolysis processing, it is same during processing
When additional some strength DC voltage；The volume ratio that lytag is mixed with iron aluminium carbon haydite is (2~5):1, voltage control
System is 0.1~0.6L/h, hydraulic detention time 6-10h in 0.5-1.4V, influent waste water speed, after processing, obtains coupling processing
Waste water；
(3) applied voltage Aerobic Process for Treatment：By step (1) processing after obtained coupling processing waste water pass through using sludge ceramsite as
Filler, carries out Aerobic Process for Treatment under the conditions of impressed DC voltage, and voltage is controlled in 0.5-1.4V, 0.1~0.6L/h of flow rate,
Hydraulic detention time 6-10h, gas-water ratio (14~18):1, the particle diameter of sludge ceramsite is 0.5-1cm, and grain density is 800-
1000kg/m3, 500~600kg/m of bulk density3, clarification and effluent is obtained after processing.
2. according to the method described in claim 1, it is characterised in that bioelectrochemistry anaerobism/light electrolysis blending one processing step
Flowed back in rapid using water after applied voltage Aerobic Process for Treatment, reflux ratio is (2-6)：1, filler is backwashed, backwashed
Cycle is 5-7 days.
3. according to the method described in claim 1, it is characterised in that described iron aluminium carbon haydite particle diameter is 0.5-1cm, particle is close
Spend for 1250-1500kg/m3, 3~8kg/m of bulk density3；Described lytag particle diameter is 2-3cm, and grain density is
750-850kg/m3, 400~500kg/m of bulk density3, 80~120cm of packed height of compound.
4. according to the method described in claim 1, it is characterised in that the volume ratio that lytag is mixed with iron aluminium carbon haydite is
(4~5):1.
5. according to the method described in claim 1, it is characterised in that described iron aluminum-carbon ternary light electrolysis haydite is with Fenton iron
Mud, aluminium powder, activated carbon are raw material, and Fenton iron cement, aluminium powder, the mass ratio of activated carbon are：(1~5)：(1~3)：(0.1~2), plus
Enter after binding agent and carry out granulation balling-up by spraying into globule, then dried raw material ball is placed at 600~650 DEG C of temperature
Anaerobic sinters 1~2h, obtained anode and cathode Integral iron aluminum-carbon ternary light electrolysis haydite, it is preferred that Fenton iron cement, aluminium powder, work
The mass ratio of property charcoal is：1：1：2, described binding agent is polyvinyl alcohol；It is described into globule be polyvinyl alcohol, carboxymethyl cellulose
In mixed solution after plain sodium and nickel sulfate hexahydrate mixing after heating water dilution, mixed solution, the mass concentration of polyvinyl alcohol is 3
~6wt%, 2~4wt% of mass concentration of sodium carboxymethylcellulose, nickel sulfate hexahydrate mass concentration are 1~2wt%；It is preferred that,
Binding agent, the mass ratio into globule and Fenton iron cement are：(1~5)：(0.1~1)：(1~5).
6. according to the method described in claim 1, it is characterised in that Ciprofloxacin influent waste water pH is 6-8, by step (2)
Wastewater pH after processing is 4-5, and the wastewater pH after step (3) processing is 6-7.
7. according to the method described in claim 1, it is characterised in that step (2), applied voltage control is in 0.8-1.2V, waste water
Water inlet speed is 0.4~0.6L/h, hydraulic detention time 8-10h.
8. according to the method described in claim 1, it is characterised in that step (3), applied voltage control is in 1.0-1.4V, waste water
Water inlet speed is 0.2~0.4L/h, hydraulic detention time 8-10h.
9. a kind of bioelectrochemistry anaerobism/light electrolysis blending coupling and intensifying handles the device of high concentration Ciprofloxacin waste water, including
Bioelectrochemistry anaerobism/microelectrolysis processing the device and aerobic treatment device being connected, described bioelectrochemistry anaerobism/micro- electricity
Solving processing unit includes filling powder in bioelectrochemistry anaerobism/micro-electrolysis stuffing area, bioelectrochemistry anaerobism/micro-electrolysis stuffing area
The compound of flyash haydite and iron aluminum-carbon ternary light electrolysis haydite, is fitted with bioelectrochemistry anaerobism/micro-electrolysis stuffing in area
Negative electrode and anode, negative electrode and anode external direct current power supply, form electro-chemical systems；Bioelectrochemistry anaerobism/micro-electrolysis stuffing area
Lower end is provided with filter plate, and the bottom of bioelectrochemistry anaerobism/microelectrolysis processing device is consolidated by adpting flange with water inlet buffering area
Fixed connection, water inlet buffering area is connected with water inlet pipe, and intake pump, bioelectrochemistry anaerobism/microelectrolysis processing are provided with water inlet pipe
The top of device, which is provided with top cover, top cover, is provided with gas outlet, and gas outlet is connected with gas storage device, and bioelectrochemistry is detested
On the side wall of oxygen/microelectrolysis processing device and positioned at being provided with delivery port between top cover and packing area；
Described aerobic treatment device includes filling sludge ceramsite in aerobic packing area, aerobic packing area, in aerobic packing area
Negative electrode and anode, negative electrode and anode external direct current power supply are fitted with, electro-chemical systems are formed；Aerobic packing area lower end is provided with filter
Aeration plate is provided with plate, filter plate, aerobic treatment device bottom is fixedly connected by flange with aerobic water inlet buffering area, aerobic
Recycling effluent mouthful and aerobic delivery port are provided with the side wall of packing area；Bioelectrochemistry anaerobism/microelectrolysis processing device goes out
The aerobic water inlet buffering area of the mouth of a river and aerobic treatment device is connected by connecting tube, and connecting tube is provided with peristaltic pump.
10. bioelectrochemistry anaerobism according to claim 9/light electrolysis blending coupling and intensifying processing high concentration Ciprofloxacin
The device of waste water, it is characterised in that the recycling effluent mouthful of aerobic treatment device passes through return duct and bioelectrochemistry anaerobism/micro- electricity
The water inlet buffering area connection of processing unit is solved, reflux pump is provided with return duct, by the effluent recycling of aerobic treatment device extremely
Handled in bioelectrochemistry anaerobism/microelectrolysis processing device, described negative electrode, anode are tubular structure, and negative electrode, anode are equal
Using carbon fibre material.
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