CN104843953B - Electrochemistry and the method for perchlorate in biological hydrogen autotrophy synergy deep conversion water - Google Patents
Electrochemistry and the method for perchlorate in biological hydrogen autotrophy synergy deep conversion water Download PDFInfo
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- CN104843953B CN104843953B CN201510304887.8A CN201510304887A CN104843953B CN 104843953 B CN104843953 B CN 104843953B CN 201510304887 A CN201510304887 A CN 201510304887A CN 104843953 B CN104843953 B CN 104843953B
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Abstract
The present invention relates to a kind of method of deep conversion water pollutant perchlorate and reactor, belong to the application field of water technology.The know-why of the present invention is to organically combine electrochemical reaction and microorganism hydrogen autotrophy, perchlorate is reduced to chlorion in the presence of catholyte produces hydrogen and hydrogen autotrophic bacteria first, then chlorion is oxidized generation Active Chlorine in the presence of electrochemical anodic oxidation, so as to realize the deep conversion of perchlorate → chlorion → Active Chlorine.The present invention makes full use of electrochemical cathode to reduce and anodic oxidation both sides reaction, the process is reduced with microorganism hydrogen autotrophy and organically combines, perchlorate is thoroughly converted into Active Chlorine, meanwhile, Active Chlorine has bactericidal action, can further lift effluent quality.The present invention substantially overcomes the shortcomings of existing biotechnology conversion perchlorate is not thorough, realizes the thorough conversion of perchlorate, and reactor spatiotemporal efficiency is high, it is easy to management and maintenance.
Description
Technical field
The present invention relates to the minimizing technology of perchlorate in water, belong to the application field of water technology.The present invention is proposed
A kind of electrochemistry and biological hydrogen the autotrophy depth that acts synergistically go the method and reactor of perchlorate in water removal, are specifically by electricity
Chemical reaction is organically combined with microorganism hydrogen autotrophy, and perchlorate is first in the presence of catholyte produces hydrogen and hydrogen autotrophic bacteria
Chlorion is reduced to, then chlorion is oxidized generation Active Chlorine in the presence of electrochemical anodic oxidation, Active Chlorine has
Sterilized, lifting water quality effect, so as to realize the deep conversion of perchlorate → chlorion → Active Chlorine.
Technical background
Instantly, due to the development of modern industry, the material containing perchlorate is widely used, and it is mainly used in rocket solid
Fuel or the field such as kinetic energy boost motor and textile dyestuff, pyrotechnics production, leather manufacture.Perchlorate has high diffusibility, height
The features such as stability, highly dissoluble and persistence, easily to water table leaching, cause water pollution.In the last few years, to high chlorine
Hydrochlorate toxicological study makes people gradually recognize that it flows into the serious consequence of environment and the serious threat to health.Drinking water
The normal function of human thyroglobulin is mainly disturbed in the harm of middle perchlorate, causes imbalance of thyroid function, influence human body
The development of development, the especially central nervous system on baby and cerebral tissue produces influence, causes amentia.In view of high chlorine
The harm of hydrochlorate, 2 months 2005, perchlorate was included in first environmental contaminants short-list by Environmental Protection Agency, it is proposed that drink
The mass concentration limit value of perchlorate is 24.5 μ g/L in water supply standard, and provides that its health reference dose is daily 0.7 μ
g/L.And China, the starting stage is still in the development of perchlorate contaminated correlative study,《Standards for drinking water quality》
(GB5749-2006) there are not relevant regulations also.But it is undeniable to be, for much coming using underground water as the area of drinking water source
Say, the purification of perchlorate brings challenges to existing water technology in water.
At present, the perchlorate of comparative maturity, which removes technique, can be divided into Physical, bioanalysis and chemical method.Physical master
To include absorption method, ion-exchange and membrane separation process.But Physical is the transfer or concentration that there occurs pollutant, not
It is thoroughly converted.Perchlorate thoroughly can be changed into chlorion by bioanalysis, be widely used at present,
It by the metabolism of microorganism by perchlorate reduction is chlorion that its principle, which is, and carbon source is needed not according to Institute of Micro-biology
Together, heterotrophism can be divided into and remove perchlorate method and autotrophy removal perchlorate method.Heterotrophism removes perchlorate method reaction speed
It hurry up, reaction efficiency is high, but sludge growth is more rapid, while needing additional organic carbon source, easily causes secondary pollution；Autotrophy with
Hydrogen removes perchlorate as desired electronic donor, converts perchlorate under conditions of DIC is as carbon source, bacterium
Propagation is relatively slow, and reaction product is simpler, cleaning, the problem of in the absence of secondary pollution.But hydrogen exist it is inflammable and explosive, be difficult fortune
It is defeated, the low problem of solubility.It is pointed out that for biological reducing perchlorate technology, what perchlorate was reduced
Product is chlorion, and high-concentration chlorine ion, which is present in the aqueous solution, can still cause the bitter saline taste of water body, the salinization of soil, pipeline corruption
The problems such as erosion, difficult plant growth.The deep conversion of perchlorate how is realized, is still a technical barrier urgently to be resolved hurrily.
The content of the invention
The perchlorate that the present invention is difficult to remove for general physical and chemical process, proposes a kind of electrochemical process and biochemistry
The perchlorate minimizing technology and relevant reactor of process synergic, realize that the depth of perchlorate-chlorion-Active Chlorine turns
Change.Instant invention overcomes the defect that biological hydrogen autotrophy removes perchlorate method, pass through the knot of electrochemistry and biological hydrogen autotrophy process
Close, form that a kind of current efficiency is high, simple to operate, be easy to the water body perchlorate removal technology applied in engineering.
The present invention know-why be：In the case where applying certain current condition, evolving hydrogen reaction, the hydrogen of precipitation occur for cathode surface
By hydrogen autotrophy perchlorate reduction bacterium using and by hydrogen autotroph reduction by the perchlorate in water be converted into chlorine from
Son.Then, chlorion is electrochemically oxidized generation Active Chlorine in anode region, and Active Chlorine has bactericidal action, can further carry
Effluent quality is risen, that is, realizes the deep conversion of perchlorate → chlorion → Active Chlorine.Said process has given full play to electrification
The effect with microorganism is learned, current efficiency is effectively improved, and fully simplify biological processing unit.
To achieve the above object, the present invention is adopted the following technical scheme that：
Perchlorate minimizing technology of the present invention is to cooperate with biological removal perchlorate integrated reacting in electrochemistry
Completed in device.The reactor includes the units such as electrode (negative electrode, anode), electrolytic cell, dc source.Dc source and negative electrode,
Connected respectively with plain conductor between anode, negative electrode, anode, which are respectively placed between electrolytic cell two ends, the two poles of the earth, uses cation exchange
Film is separated by into cathode zone and anode region.The cathode zone of electrolytic cell is also the biochemical reaction zone of microbial action simultaneously,
Cathode zone is initially entered by the raw water of perchlorate contaminated, then into anode region until final outflow water, device is continuous
Pass in and out aqueous mode；Reduced in cathode zone inoculated and cultured concentration range in 500mg/L-20 000mg/L perchlorate hydrogen autotrophy
Bacterium；Direct current of the voltage range between 0.5V-100V is passed at two kinds of electrode two ends, in the presence of direct current, negative electrode production
Perchlorate reduction is chlorion using electrolytic hydrogen production by raw hydrogen, microorganism；Then chlorion is oxidized life in anode region
Viability chlorine, so as to realize the deep conversion of perchlorate → chlorion → Active Chlorine.The Active Chlorine of generation can be carried out to water outlet
Further sterilizing processing.
The present invention is higher using current efficiency, and performance suitable material is used as reactor electrodes.Anode uses nickel plate, titanium
The pole plate that any one material such as plate, ruthenium plate or titanium-ruthenium is made；Negative electrode uses stainless steel plate, iron plate, aluminium sheet, copper coin, graphite
The pole plate that any one material such as plate, carbon fiber sheet, nickel plate, titanium plate or titanium-ruthenium is made.
Foregoing electrolytic cell, the region of negative and positive two can be carried out closed using water seal.Cathode zone can use activated carbon, nothing
The materials such as bituminous coal, soft cellulose filler, mandruka adhere to thereon as bio-carrier, hydrogen autotrophic bacterium；Or use microfiltration membranes mistake
Hydrogen autotrophic bacterium is retained in cathode zone by the form of filter.The microbe stuffing of aufwuch hydrogen autotrophic bacterium directly connects with negative electrode
Touch, or hydrogen autotrophic bacterium mixed liquor is directly contacted with negative electrode.
The present invention can be run under underload and high-load condition.For the relatively low perchlorate of concentration, apply electric current
Relatively low, less, water inlet enters anode region hair to negative and positive the two poles of the earth region pH value fluctuating range after cathode zone carries out biochemical reaction
Raw electrochemical oxidation reactions, then can directly water outlet (as shown in Figure 1)；For the perchlorate of high concentration, apply electric current compared with
Height, the two poles of the earth region pH value fluctuating range is larger, easily influence is produced on microbial biochemical reaction, to stablize negative and positive the two poles of the earth region
PH value, can use the operator scheme of inner loop, i.e. can enter anode region after the part solution of negative electrode chamber region is degassed, together
When anode region part solution it is degassed after can enter cathode zone (as shown in Figure 2).
Perchlorate minimizing technology of the present invention can handle the perchlorate contaminated water body for lacking organic carbon source, bag
Include underground water, surface water and trade effluent.The prominent advantage of the present invention is：Current efficiency is high, and reaction speed is fast, biological treatment list
Member simplifies, it is easy to operate, floor space is small.In addition, reactor of the present invention can be with multigroup used in parallel to expand its disposal ability.
Brief description of the drawings：
Fig. 1 flow reactor schematic diagrames of the present invention (cathode zone uses biologic packing material fixation of microbe)
Fig. 2 continuous degassing inner circulation reactor schematic diagrames of the present invention (cathode zone retains microorganism using membrane module)
Reference：
1 enters water pot；2 intake pumps；3 dc sources；4 cation-exchange membranes；5 negative electrodes；6 anodes；7 biologic packing materials；8 water seals；9
Water outlet；10 hydrogen autotrophic bacterium mixed liquors；11 micro-filtration membrane modules；12 microorganisms are flowed back；13 degassers；14 agitators
Embodiment
Embodiment 1：
Reactor cathode chamber effective volume 600mL.Using porous nickel plate as negative electrode, titanium ruthenium net keeps cloudy as anode
Pole room hydrogen autotrophy perchlorate degraded sludge concentration 5000mg/L, applies electric current 50mA, works as ClO4 -Initial concentration 10mg/L, is stopped
During time 11h, reactor ClO4 -Clearance ＞ 90%, Active Chlorine conversion ratio ＞ 95%.
Embodiment 2：
Reactor cathode chamber effective volume 600mL.Using stainless steel plate as negative electrode, titanium ruthenium net keeps cloudy as anode
Pole room hydrogen autotrophy perchlorate sludge concentration 1000mg/L, applies electric current 100mA, works as ClO4 -Initial concentration 10mg/L, during stop
Between 8h, reactor ClO4 -Clearance ＞ 95%, Active Chlorine conversion ratio ＞ 98%, and the accumulation without intermediate product.
Embodiment 3：
Using continuous degassing inner circulation reactor, titanium plate is as negative electrode, and titanium ruthenium net is as anode, and reactor cathode chamber is effective
Volume 600mL, cathode chamber hydrogen autotrophy perchlorate degraded sludge concentration 1000mg/L, applies electric current 50mA.Work as ClO4 -It is initial dense
20mg/L is spent, nitrate recirculation ratio is 0.5, during residence time 16h, reactor ClO4 -Clearance ＞ 95%, Active Chlorine conversion ratio ＞
98%, and the accumulation without intermediate product.
Claims (5)
1. a kind of electrochemistry and the method for perchlorate in biological hydrogen autotrophy synergy deep conversion water, it is characterised in that：Adopt
DC electrolysis reaction system is divided into negative electrode and anode region with cation-exchange membrane, by perchlorate contaminated raw water first
Into cathode zone, then into anode region until final outflow water, device is aqueous mode of being back to back；In cathode zone inoculation
Cultivate perchlorate hydrogen autotrophy reducing bacteria of the concentration range in 500mg/L-20 000mg/L；In the presence of direct current, negative electrode
Hydrogen is produced, perchlorate reduction is chlorion using electrolytic hydrogen production by microorganism；Then chlorion is oxidized in anode region
Active Chlorine is generated, that is, realizes the deep conversion of perchlorate → chlorion → Active Chlorine.
2. in accordance with the method for claim 1, it is characterised in that cathode zone is filled out using activated carbon, anthracite, soft fiber
One or more materials in material, mandruka are as bio-carrier, and hydrogen autotrophic bacterium adheres to thereon；Or using micro-filtrate membrane filtration
Hydrogen autotrophic bacterium is retained in cathode zone by form.
3. in accordance with the method for claim 1, it is characterised in that electrochemistry collaboration biological agent passes through in electrolytic cell negative and positive two
Pole passes to voltage range and is achieved in 0.05-100V dc source.
4. in accordance with the method for claim 1, it is characterised in that anode uses any one in nickel plate, titanium plate, ruthenium plate or titanium-ruthenium
Plant the pole plate that material is made；Negative electrode using stainless steel plate, iron plate, aluminium sheet, copper coin, graphite cake, carbon fiber sheet, nickel plate, titanium plate or
The pole plate that any one material is made in titanium-ruthenium.
5. in accordance with the method for claim 1, it is characterised in that can be real after negative electrode and the degassed device degassing of anode region solution
Anode region can be entered after the solution degassing of existing inner loop, i.e. negative electrode chamber region, while can after the solution degassing of anode region
Into cathode zone, so as to stablize the pH value of two region solution.
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| CN105236590A (en) * | 2015-11-11 | 2016-01-13 | 河南工业大学 | Method for deep degrading perchlorate in water through synergism of microorganism heterotrophism and electrochemistry hydrogen autotrophy |
| CN105253992B (en) * | 2015-11-11 | 2019-03-05 | 河南工业大学 | The method that electrodialysis-ion exchange membrane bioreactor removes perchlorate in water removal |
| CN113354068A (en) * | 2021-06-03 | 2021-09-07 | 郑州大学 | Conductive medium assisted double-biological-chamber electrochemical membrane bioreactor and application method thereof |
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| WO2008132296A2 (en) * | 2007-03-02 | 2008-11-06 | Degremont | Method and equipment for processing waste water containing sulphides and ammonium |
| CN102340015A (en) * | 2011-07-28 | 2012-02-01 | 西安交通大学 | Microorganism electrochemical system capable of realizing electricity generation, hydrogen generation and sewage treatment simultaneously |
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| CN1629085A (en) * | 2003-12-16 | 2005-06-22 | 中国科学院生态环境研究中心 | Electrochemical oxidation process for removing algae toxins from water |
| CN102219328A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院生态环境研究中心 | Photoelectric integrated reactor capable of deeply treating garbage leachate |
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| WO2008132296A2 (en) * | 2007-03-02 | 2008-11-06 | Degremont | Method and equipment for processing waste water containing sulphides and ammonium |
| CN102340015A (en) * | 2011-07-28 | 2012-02-01 | 西安交通大学 | Microorganism electrochemical system capable of realizing electricity generation, hydrogen generation and sewage treatment simultaneously |
| CN104141165A (en) * | 2013-05-10 | 2014-11-12 | 盛美半导体设备（上海）有限公司 | Polishing solution recycling apparatus |
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