CN105000662A - Method used for removing antibiotics in breeding industry wastewater via anaerobic self-electrolysis - Google Patents
Method used for removing antibiotics in breeding industry wastewater via anaerobic self-electrolysis Download PDFInfo
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Abstract
The invention discloses a method used for removing antibiotics in breeding industry wastewater via anaerobic self-electrolysis, and applications thereof. The method comprises following steps: (1) breeding industry wastewater is mixed with an anaerobic granular sludge supernate, an anaerobic self-electrolysis reactor is connected with an external resistor, and is activated in a sequencing batch mode until a maximum value of an output voltage is reached and the output voltage is stabilized so as to realize starting of a reaction system; and (2) breeding industry wastewater is taken as a substrate so as to realize continuous flow operation of the anaerobic self-electrolysis reactor, and operation of the anaerobic self-electrolysis system is stabilized so as to remove antibiotics in breeding industry wastewater. According to the method used for processing breeding industry wastewater via anaerobic self-electrolysis, antibiotics can be removed effectively without external voltage, problems of conventional anaerobic technology in antibiotic degradation are solved; operation conditions of the method are mild; operation is generally carried out at normal temperature under normal pressure and in a close-to-neutral environment; maintenance cost is low; and safety is high. The method is economical, and is friendly to the environment; and prospect is promising.
Description
Technical field
The invention belongs to environmental pollution biological treatment and bioenergy technical field, be specifically related to a kind of effectively to remove in breeding wastewater antibiotic anaerobism from electrolytic processing method.
Background technology
In the later stage forties 20th century, since finding that microbiotic to have the effect of growth promoting effects to animal, different sorts microbiotic adds in poultry industry feed in succession, promoting growth of animals or poultry, reduces disease thus reaches the object of volume increase, weightening finish, the raising price of deed.The annual approximately XX ton microbiotic of China adds livestock and poultry breeding industry feed to, mainly comprises tetracyclines, sulfamido, macrolide and fluoroquinolone antibiotics.Major part microbiotic cannot degraded and absorbed in animal body, is all discharged into breeding wastewater by virgin state or metabolite form.In recent years, rapidly, the breeding wastewater total amount of annual discharge, more than 1,900,000,000 t, becomes the emerging source of pollution of big and medium-sized cities and the third-largest source of pollution after trade effluent, sanitary sewage to China's poultry industry development.Then livestock breeding wastewater microbiotic pollutes also to a more serious degree, and the annual nearly 1800-5400t microbiotic of China is discharged into contaminate environment in the middle of environment.Antibiotic existence can work the mischief to surrounding enviroment, causes that bacterial drug resistance produces, animal product drug residue exceeds standard and the series of problems such as environmental pollution, brings significant damage to Animal husbandry production and human health.
Breeding wastewater is a class high concentrated organic wastewater, has the features such as colourity is large, stink large, high loading, biodegradability are strong.Process at present about them is confined to conventional biochemical treatment mostly, comprises Ecologize technology and " solid-liquid separation-anaerobic-aerobic " manual handling technique.But breeding wastewater exists larger veterinary antibiotic pollution load, microbiotic has serious hindrance to traditional anaerobic technology process breeding wastewater stability simultaneously, and standard biochemical methods process breeding wastewater difficulty is expanded further.Microbiotic how effectively in degraded removal waste water, the large major issue preventing the harm of microbiotic to water body environment from being process breeding wastewater.
Summary of the invention
The present invention overcomes the defect of above-mentioned cultivating wastewater purification mode, provides a kind of and effectively to remove in waste water antibiotic anaerobism from electrolysis breeding wastewater method.Non-energy-consumption light electrolysis, microbiological deterioration and bioelectrochemistry technique combine together by this method, remove in breeding wastewater while pollutent in anaerobism from electrolysis, effectively remove the microbiotic in waste water.
The present invention realizes mainly through following technological step:
A kind of anaerobism removes antibiotic method in breeding wastewater from electrolysis, comprises the steps:
(1) mixed with anaerobic grain sludge supernatant liquor by breeding wastewater, outer meeting resistance, sequence batch (starts anaerobism from electrolysis reactor, until output voltage reaches maximum value and stablizes, realization response system starts;
(2) be that substrate Continuous Flow runs anaerobism from electrolysis reactor with breeding wastewater, stablize anaerobism and run from electrolysis system, the microbiotic in breeding wastewater can be removed.
In step (1), between the starting period, the volume ratio of described breeding wastewater and anaerobic grain sludge supernatant liquor is 1:1.
Voltage described in step (1) adopts Keithley 2700 data acquisition unit to gather.
Step (2) described breeding wastewater is at least 2d at the hydraulic detention time of anaerobism in electrolysis system.
Step (1) described output voltage reaches maximum value and stablizes at least needs 12d.
Described anaerobism controls at 30 ± 5 DEG C from the temperature that electrolysis reactor runs.
Described anaerobism is cylinder tetrafluoroethylene Glass tubing from electrolysis reactor, and anode is the carbon felt of encapsulation reaction device inwall and the activated carbon granule be filled in reactor, described carbon felt Nitric Acid Modified mistake, activated carbon granule acetone pre-treatment, Nitric Acid Modified mistake; Air cathode is for being loaded with 0 ~ 12.0mg/cm
2mnO
2the carbon cloth of catalyzer is one deck cationic exchange membrane inside negative electrode, makes electronics collector between anode and cathode with titanium silk.
The method of described carbon felt Nitric Acid Modified is: (1) soaks carbon felt 2 ~ 4h with acetone, then uses washed with de-ionized water 3 ~ 5 times, then soaks with deionized water, boil carbon felt 2 ~ 4h, finally dries; (2) pretreated carbon felt anode is put into some beakers, use dense HNO
3soak 4 ~ 6h, then with after deionized water wash to neutrality, dry in 120 DEG C of baking ovens and take out.
The method of described activated carbon granule Nitric Acid Modified is: gac is put into some beakers, uses dense HNO
3soak 4 ~ 6h, then with after deionized water wash to neutrality, dry in 120 DEG C of baking ovens and take out.
The diameter of described activated carbon granule is 3 ~ 5mm, and loading level is 300g.
Described cathode load MnO
2the carrying capacity of catalyzer is 0 ~ 8.0mg/cm
2.
Described microbiotic comprises duomycin, sulphamethazine, Roxithromycin, norfloxicin.
The present invention compared with prior art tool has the following advantages and beneficial effect:
(1) breeding wastewater anaerobism is in electrolytic process, and microbiotic exists restraining effect but little on effluent quality impact on anaerobism from the electricity generation performance of electrolytic process, and anaerobism effectively can remove microbiotic from electrolytic process simultaneously.
(2) breeding wastewater anaerobism is gentle from electrolysis mode operational condition, and generally work in normal temperature, normal pressure, close neutral environment, this makes battery maintenance cost low, high safety.
Accompanying drawing explanation
Fig. 1 to represent in the embodiment of the present invention 1 anaerobism from electrolysis reactor at starting period voltage curve over time.
Fig. 2 represents in the embodiment of the present invention 1 anaerobism from the power density of electrolysis reactor under Continuous Flow state and polarization curve.
Fig. 3 (a) (b) (c) (d) (e) (f) represents embodiment 2 reactor output voltage respectively, and COD, total phosphorus, total nitrogen, nitric nitrogen and ammonia nitrogen removal frank be change curve under the four classes different microbiotic stage.
Fig. 4 (a) (b) (c) (d) (e) (f) represents embodiment 3 reactor output voltage respectively, and COD, total phosphorus, total nitrogen, nitric nitrogen and ammonia nitrogen removal frank be change curve under the different concns gradient microbiotic stage.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.The present invention adopts analog culture waste water to investigate the microbiotic of anaerobism in electrolysis system and removes situation and microbiotic to the impact of breeding wastewater anaerobism from electrolysis.Analog culture waste component includes glucose 4.7g/L, ammonium chloride 2.0g/L, Sodium phosphate dibasic 3.2g/L, SODIUM PHOSPHATE, MONOBASIC 1.8g/L, Repone K 0.13g/L SODIUMNITRATE 0.8g/L.
Embodiment 1
A kind of breeding wastewater anaerobism removes antibiotic method from electrolysis, and concrete operation step is as follows:
(1) mixed by 1:1 volume ratio with anaerobic grain sludge supernatant liquor by analog culture waste water, under extrernal resistance 1000 Ω, 30 ± 1 DEG C of constant temperatures, sequence batch (starts anaerobism from electrolysis reactor.Described anaerobism is from electrolysis reactor, and form primarily of two portions, cubic capacity is at 1200mL.Top is columniform Glass tubing, and Glass tubing outer wall perforate footpath is the aperture of 1mm, and its percentage of open area is 15%, and bottom is inverted conical body, and cylinder bottom arranges water-in, and side, top sets out the mouth of a river, and water-in and water outlet diameter are about 4mm.Form anolyte compartment inside reactor, cationic exchange membrane is wrapped up successively in outside, cathode material.The carbon felt that anode material comprises parcel cylindrical glass inside pipe wall ((is of a size of 16cm × 20cm, thickness is 8mm) and filling reactor in activated carbon granule (particle diameter is 2 ~ 5mm, loading level is 300g) composition, described carbon felt Nitric Acid Modified mistake, activated carbon granule acetone pre-treatment, Nitric Acid Modified mistake.Cylindrical glass tube and cone joining place arrange porous circular baffle plate, in case activated carbon granule blocking water-in.Anode material is filled into after in reactor, and the useful volume (NAC) of reactor anolyte compartment is 250mL.Air cathode is for carrying 8.0mg/cm
2mnO
2(be of a size of 32cm × 16cm, useful area is 500cm to the carbon cloth of catalyzer
2).Electronics collector is made with titanium silk between anode and cathode.
The method of described carbon felt Nitric Acid Modified is: (1) soaks carbon felt 3h with acetone, then uses washed with de-ionized water 3 ~ 5 times, then soaks with deionized water, boil carbon felt 3h (changing water 1 time every 0.5h), finally dries; (2) pretreated carbon felt anode is put into some beakers, use dense HNO
3soak 5h, then with after deionized water wash to neutrality, in 120 DEG C of baking ovens, dry 2h take out for subsequent use.
The method of described activated carbon granule Nitric Acid Modified is: gac is put into some beakers, uses dense HNO
3soak 5h, then with after deionized water wash to neutrality, in 120 DEG C of baking ovens, dry 2h take out for subsequent use.
(2) through the starting period of 79d, the operational mode of reactor is changed to continuously streamed by batch-type rotary.Under be 1000 Ω, service temperature T being the condition of 30 ± 1 DEG C at outer meeting resistance, by peristaltic pump, analog culture waste water is entered reactor with the flow velocity of 7.81ml/h (corresponding hydraulic detention time HRT is for 4d) continuously from reactor bottom, after for some time steady running (at least three HRT), successfully realize simulated wastewater anaerobism and remove from electrolysis.
(3) after for some time steady running, by changing outer meeting resistance, from electrolysis reactor, polarization curve being carried out to anaerobism, determining power density.
(4) anaerobism automatically records storage every 80s by Keithley 2700 data collecting system from the output voltage (U) of electrolysis treatment waste water.The polarization curve of MFC and internal resistance adopt steady-state discharge method to measure, namely within the scope of 10 ~ 90000 Ω regulating resistance until there is stable magnitude of voltage (each external resistance at least repeats 3 times), again according to Ohm's law I=U/R calculating current value, and then acquisition polarization curve, the ohmic polarization district partial data of polarization curve is carried out linear goal programming, and gained slope is the internal resistance of battery.Power density (P) utilizes formula P=IU/V to calculate.Wherein, V is battery useful volume.
Result is as follows:
(1) cultivate operation anaerobism from electrolysis reactor through 79d intermittent type, electrogenesis microbial film is successful enrichment on anode material surface.And parallel anaerobism is 0.574V, 0.565V from the final regulated output voltage of electrolysis reactor ASE-112, ASE-116, has good circulation ratio.
(2) anaerobism obtains maximum power density from electrolysis reactor ASE-112, ASE-116 under Continuous Flow condition is 5.78W/m
3and 5.82W/m
3.Its internal resistance is respectively 28.06 Ω, 29.38 Ω.
The present embodiment result illustrates: anaerobism successfully starts from electrolysis reactor, can be follow-up investigation microbiotic and lays the foundation from electrolysis removal situation in anaerobism from the impact of electrolysis system electrogenesis scavenging effect and microbiotic on anaerobism.
Embodiment 2
The different microbiotic of four classes remove situation and on the impact of breeding wastewater anaerobism from electrolysis, concrete implementation step is as follows at the microbiotic of anaerobism in electrolysis system:
(1), under be 1000 Ω, service temperature T being the condition of 30 ± 1 DEG C at outer meeting resistance, reactor is run in Continuous Flow mode, output voltage continous-stable at least three HRT;
(2) adopt superposition ground mode successively to add to manual simulation's breeding wastewater by duomycin (tetracyclines), sulphamethazine (sulfamido), Roxithromycin (macrolide), norfloxicin (fluoroquinolones) four kinds of exogenous microbiotic of typical case, will not run anaerobism containing antibiotic manual simulation's breeding wastewater is stage A from electrolysis reactor; To be stage B to run anaerobism from electrolysis reactor containing manual simulation's breeding wastewater of duomycin (15 μ g/L); Be stage C to run anaerobism containing manual simulation's breeding wastewater of duomycin (15 μ g/L), sulphamethazine (10 μ g/L) from electrolysis reactor; Running anaerobism from electrolysis reactor with the manual simulation's breeding wastewater containing duomycin (15 μ g/L), sulphamethazine (10 μ g/L) and Roxithromycin (6 μ g/L) is stage D; Running anaerobism from electrolysis reactor with the manual simulation's breeding wastewater containing duomycin (15 μ g/L), sulphamethazine (10 μ g/L), Roxithromycin (6 μ g/L) and norfloxicin (6 μ g/L) is stage E, each stage output voltage continous-stable at least three HRT;
(3) anaerobism under the on-line monitoring different residence time is from the electrochemistry index of electrolysis reactor process waste water, and its measuring method as described in Example 1.
(4), while reactor electrochemistry index carries out on-line monitoring under to the different residence time, also the COD in Inlet and outlet water, ammonia nitrogen, nitre nitrogen, total nitrogen and total phosphorus are measured.Wherein, COD and nitrate nitrogen measure by environment protection industry standard rapid-digestion spectrophotometry (HJ/T399-2007) and ultraviolet spectrophotometry (HJ/T346-2007) respectively; Ammonia nitrogen and total nitrogen are cleared up ultraviolet spectrophotometry (GB11894-89) by environmental protection standard Berthelot spectrophotometry (HJ535-2009) and national standard alkaline chitinase respectively and are measured.Total phosphorus measures by national standard ammonium molybdate spectrophotometric method (GB11893-89).
(5) add different steps at microbiotic, except measuring Conventional waste water contamination index, Inlet and outlet water microbiotic being measured equally, before water determination, carrying out corresponding pre-treatment, adopt LC-MS to carry out quantitative analysis.LC-MS analytical instrument used is Agilent 1200SL series RRLC/6410B TripleQuard MS rapidly and efficiently liquid chromatography/series connection quadrupole GC-MS.
Result is as follows:
(1) four kind of different classes of microbiotic (duomycin, sulphamethazine, Roxithromycin and norfloxicin) on the impact of anaerobism from electrolysis electricity generation performance, the stage A not having exogenous microbiotic to add, anaerobism is from electrolysis reactor ASE-112, ASE-116 output voltage is basically stable at 0.549V, 0.550V, antibioticly to add successively along with exogenous, output voltage along with often kind antibiotic add to have significantly reduce, when four class microbiotic are all added in analog culture waste water, reactor A SE-112, the output voltage of ASE-116 is reduced to 0.419V, 0.418V.Illustrate that tetracycline antibiotics duomycin, sulfa antibiotics sulphamethazine, macrolide antibiotic Roxithromycin and fluoroquinolone antibiotics norfloxicin all have restraining effect to anaerobism from electrolysis electricity generation performance.
(2) anaerobism is under electrolysis tech treatment of simulated breeding wastewater different steps, COD, total phosphorus, total nitrogen, ammonia nitrogen and nitrate nitrogen in Inlet and outlet water are measured, can find, water outlet COD and total phosphorus removal effect slightly improve, and nitrogen removal rate decreases after adding microbiotic, the fluctuation of nitric nitrogen removal effect is little, and ammonia nitrogen removal effect increases.But the pollutant removal index changes such as COD, total phosphorus, total nitrogen, ammonia nitrogen, nitric nitrogen are less, COD clearance is between 96 ~ 99%, total tp removal rate fluctuates between 55% ~ 60%, between nitrogen removal rate 70 ~ 80%, ammonia nitrogen removal frank is between 59 ~ 72%, and nitric nitrogen clearance is between 95 ~ 97%.Illustrate that the antibiotic interpolation of duomycin, sulphamethazine, Roxithromycin and norfloxicin four class causes anaerobism slightly to take a turn for the better from electrolysis system effluent quality, but its impact is less.
(3) under four class microbiotic successively interpolation stage, anaerobism is in electrolysis reactor treatment of simulated breeding wastewater process, and duomycin, Roxithromycin, sulphamethazine and norfloxicin are all efficiently removed.In water outlet, duomycin, Roxithromycin and blood concentration norfloxacin all do not detect, sulphamethazine still has residual, but removal effect is quite obvious, and its water outlet sulphamethazine concentration is all at 0.1 below μ g/L, and concrete clearance can reach 99.9%.Illustrate in the anaerobism of adding without external voltage in electrolysis system, all kinds of antibiotic removal reaches good result.
The present embodiment illustrates and is adding duomycin, sulphamethazine, Roxithromycin and norfloxicin four successively in class microbiotic process, and anaerobism reduces gradually from electrolysis reactor electricity generation performance, and little from the impact of electrolysis system effluent quality on anaerobism.In water outlet simultaneously, duomycin, Roxithromycin, sulphamethazine and norfloxicin are all efficiently removed equally.
Table 1 executes the different microbiotic of example four class in anaerobism removal effect in electrolysis breeding wastewater process
Remarks: stage A, antibiotic-free is added into analog culture waste water;
Stage B, duomycin is added into analog culture waste water;
Stage C, duomycin, sulphamethazine are added into analog culture waste water;
Stage D, duomycin, sulphamethazine, Roxithromycin are added into analog culture waste water;
Stage E, duomycin, sulphamethazine, Roxithromycin, norfloxicin are added into analog culture waste water.
Embodiment 3
Different concns gradient microbiotic removes situation and on the impact of analog culture anaerobic waste water from electrolysis, concrete implementation step is as follows at the microbiotic of anaerobism in electrolysis system:
(1), under be 1000 Ω, service temperature T being the condition of 30 ± 1 DEG C at outer meeting resistance, reactor is run in Continuous Flow mode, output voltage continous-stable at least three HRT.
(2) four class microbiotic of high, medium and low three kinds of different concns gradients are added into successively in analog culture waste water as water inlet.Wherein, will not run anaerobism containing antibiotic manual simulation's breeding wastewater is stage A from electrolysis reactor, will to contain duomycin (45 μ g/L), sulphamethazine (30 μ g/L), it is stage F that manual simulation's breeding wastewater of Roxithromycin (18 μ g/L) and norfloxicin (18 μ g/L) runs ASE reactor, to contain duomycin (15 μ g/L), sulphamethazine (10 μ g/L), it is stage G that manual simulation's breeding wastewater of Roxithromycin (6 μ g/L) and norfloxicin (6 μ g/L) runs ASE reactor, to contain duomycin (3 μ g/L), sulphamethazine (2 μ g/L), it is stage H that manual simulation's breeding wastewater of Roxithromycin (1.2 μ g/L) and norfloxicin (1.2 μ g/L) runs ASE reactor, reactor output voltage continous-stable at least three HRT.
(3) anaerobism under the on-line monitoring different residence time is from the electrochemistry index of electrolysis reactor process waste water, and its measuring method as described in Example 1.
(4), while reactor electrochemistry index carries out on-line monitoring under to the different residence time, also the COD in Inlet and outlet water, ammonia nitrogen, nitre nitrogen, total nitrogen and total phosphorus are measured.Its measuring method as described in Example 2.
(5) measure Inlet and outlet water microbiotic, its measuring method as described in Example 2.
Result is as follows:
(1) under different concns gradient microbiotic on the impact of ASE electricity generation performance, with the stage F that high density microbiotic runs, the output voltage stabilization of reactor A SE-112, ASE-116 is at 0.413V, 0.416V, along with the reduction gradually of antibiotic concentration, anaerobism slowly increases from the output voltage of electrolysis reactor ASE-112, ASE-116, at stage G, the output voltage stabilization of ASE-112, ASE-116 is at 0.430V, 0.429V; At the output voltage stabilization of stage H, reactor A SE-112, ASE-116 at 0.447V, 0.445V.Reduction gradually along with antibiotic concentration is described, anaerobism increases gradually to some extent from electrolysis electricity generation performance.
(2) to while under different antibiotic concentration gradient step, the electrochemistry index of reactor carries out on-line monitoring, also the COD in Inlet and outlet water, total nitrogen, ammonia nitrogen and nitrate nitrogen are measured.Wherein, water outlet COD clearance all can reach 98%-99%, total tp removal rate can reduce with antibiotic concentration rise to 73% by 52%.Nitrogen removal rate is by 77% to 84%.Nitric nitrogen clearance is at 93.28%-95.05%.Ammonia nitrogen removal frank then increases to 88% along with antibiotic concentration reduces by 57%.Illustrate in different antibiotic concentration gradient Imitating breeding wastewater anaerobism in electrolytic process, along with antibiotic concentration reduces, effluent quality effect increases, wherein be mainly manifested in the clearance of ammonia nitrogen and total phosphorus, and the removal effect of COD, total nitrogen and nitric nitrogen also slightly takes a turn for the better in water outlet, but DeGrain.
(3) at different antibiotic concentration gradient step, anaerobism is in electrolysis reactor treatment of simulated breeding wastewater process, and duomycin, Roxithromycin, sulphamethazine and norfloxicin are all efficiently removed equally.In water outlet, duomycin, Roxithromycin and blood concentration norfloxacin all do not detect, sulphamethazine still has residual, but removal effect is quite obvious, and its water outlet sulphamethazine concentration is all at 0.1 below μ g/L, and concrete clearance can reach 99.9%.Illustrate in the anaerobism of adding without external voltage in electrolysis system, all kinds of antibiotic removal reaches good result.
The present embodiment illustrates when investigation different concns gradient microbiotic affects from electrolysis system anaerobism, can find along with antibiotic concentration constantly reduces, anaerobism increases to some extent from electrolysis system electricity generation performance, effluent quality effect increases simultaneously, is wherein mainly manifested in the clearance of ammonia nitrogen and total phosphorus.And duomycin, Roxithromycin, sulphamethazine and norfloxicin are all efficiently removed.
Table 2 the present embodiment four class different concns gradient microbiotic is in anaerobism removal effect in electrolytic simulation breeding wastewater process
Remarks: stage A, not containing microbiotic analog culture waste water;
Stage F, the duomycin under high concentration gradient, sulphamethazine, Roxithromycin, norfloxicin are added into analog culture waste water;
Stage G, the duomycin under middle concentration gradient, sulphamethazine, Roxithromycin, norfloxicin are added into analog culture waste water;
Stage H, the duomycin under lower concentration gradient, sulphamethazine, Roxithromycin, norfloxicin are added into analog culture waste water.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. anaerobism removes an antibiotic method in breeding wastewater from electrolysis, it is characterized in that, comprises the steps:
(1) mixed with anaerobic grain sludge supernatant liquor by breeding wastewater, outer meeting resistance, sequence batch (starts anaerobism from electrolysis reactor, until output voltage reaches maximum value and stablizes, realization response system starts;
(2) be that substrate Continuous Flow runs anaerobism from electrolysis reactor with breeding wastewater, stablize anaerobism and run from electrolysis system, the microbiotic in breeding wastewater can be removed.
2. method according to claim 1, is characterized in that, in step (1), between the starting period, the volume ratio of described breeding wastewater and anaerobic grain sludge supernatant liquor is 1:1.
3. method according to claim 1, is characterized in that, step (2) described breeding wastewater is at least 2d at the hydraulic detention time of anaerobism in electrolysis system.
4. method according to claim 1, is characterized in that, step (1) described output voltage reaches maximum value and stablizes at least needs 12d.
5. method according to claim 1, is characterized in that, described anaerobism controls at 30 ± 5 DEG C from the temperature that electrolysis reactor runs.
6. the method according to any one of Claims 1 to 5, it is characterized in that, described anaerobism is cylinder tetrafluoroethylene Glass tubing from electrolysis reactor, anode is the carbon felt of encapsulation reaction device inwall and the activated carbon granule be filled in reactor, described carbon felt Nitric Acid Modified mistake, activated carbon granule acetone pre-treatment, Nitric Acid Modified mistake; Air cathode is for being loaded with 0 ~ 12.0mg/cm
2mnO
2the carbon cloth of catalyzer is one deck cationic exchange membrane inside negative electrode, makes electronics collector between anode and cathode with titanium silk.
7. method according to claim 6, is characterized in that,
The method of described carbon felt Nitric Acid Modified is: (1) soaks carbon felt 2 ~ 4h with acetone, then uses washed with de-ionized water 3 ~ 5 times, then soaks with deionized water, boil carbon felt 2 ~ 4h, finally dries; (2) pretreated carbon felt anode is put into some beakers, use dense HNO
3soak 4 ~ 6h, then with after deionized water wash to neutrality, dry in 120 DEG C of baking ovens and take out.
The method of described activated carbon granule Nitric Acid Modified is: gac is put into some beakers, uses dense HNO
3soak 4 ~ 6h, then with after deionized water wash to neutrality, dry in 120 DEG C of baking ovens and take out.
8. the method according to claim 6 or 7, is characterized in that, the diameter of described activated carbon granule is 3 ~ 5mm.
9. the method according to claim 6 or 7, is characterized in that, described cathode load MnO
2the carrying capacity of catalyzer is 0 ~ 8.0mg/cm
2.
10. the method according to any one of Claims 1 to 5, is characterized in that, described microbiotic comprises duomycin, sulphamethazine, Roxithromycin, norfloxicin.
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Application publication date: 20151028 |