CN104843953A - Method for deeply transforming perchlorate contained in water through synergistic effect of electrochemistry and biological hydrogen autotrophy and reactor - Google Patents
Method for deeply transforming perchlorate contained in water through synergistic effect of electrochemistry and biological hydrogen autotrophy and reactor Download PDFInfo
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Abstract
The invention relates to a method for deeply transforming water pollutant perchlorate and a reactor, and belongs to the field of application of a water treatment technology. According to a technical principle, electrochemical reaction and microbial hydrogen autotrophy are organically combined; the perchlorate is firstly reduced into a chloride ion under the action of a cathode producing hydrogen and hydrogen autotrophic bacteria through electrolysis, then the chloride ion is oxidized into active chlorine under the action of electrochemical anodic oxidation, so that the deep transformation from the perchlorate to the chloride ion to the active chlorine is realized. The method disclosed by the invention can be used for thoroughly transforming the perchlorate into the active chlorine by organically combining the process with microbial hydrogen autotrophy reduction by sufficiently utilizing two aspects of reaction, namely electrochemical cathodic reduction and anodic oxidation, and can be used for further enhancing the quality of effluent water because the active chlorine has bactericidal effect. The method disclosed by the invention can be used for sufficiently overcoming the defects of non-thorough perchlorate transformation of the tradition biological technology and the like and realizing the thorough transformation of the perchlorate. The reactor disclosed by the invention has the advantages of high time and space efficiency and easy management and maintenance.
Description
Technical field
The present invention relates to the minimizing technology of perchlorate in water, belong to the Application Areas of water technology.The present invention proposes a kind of electrochemistry and the biological hydrogen autotrophy degree of depth that acts synergistically and remove method and the reactor of perchlorate in water, specifically electrochemical reaction and microorganism hydrogen autotrophy are organically combined, perchlorate is reduced to chlorion first produce the effect of hydrogen and hydrogen autotrophic bacteria at catholyte under, then chlorion oxidized generation reactive chlorine under the effect of electrochemical anodic oxidation, reactive chlorine has sterilization, promotes the effect of water quality, thus realizes the deep conversion of perchlorate → chlorion → reactive chlorine.
Technical background
Instantly, due to the development of modern industry, the material containing perchlorate widely uses, and it is mainly used in ballistite or the field such as kinetic energy thruster and textile dyestuff, pyrotechnics production, leather manufacture.Perchlorate has the features such as high diffusibility, high stability, high resolution and persistence, easily to Water table leaching, causes water pollution.In the last few years, it flows into the serious consequence of environment and the serious threat to HUMAN HEALTH to perchlorate toxicological study, people to be recognized gradually.The normal function of human thyroglobulin is mainly disturbed in the harm of Perchlorate in Drinking Water, causes imbalance of thyroid function, affects the growth of human body, especially has an impact to the unify growth of cerebral tissue of the central nervous system of baby, causes amentia.In view of the harm of perchlorate, in February, 2005, perchlorate is listed in first environmental pollutant short-list by Environmental Protection Agency, and in suggestion drinking water standard, the mass concentration limit value of perchlorate is 24.5 μ g/L, and specifies that its HUMAN HEALTH reference dose is μ g/L every day 0.7.And China, be still in the starting stage to carrying out of perchlorate contaminated correlative study, " drinking water sanitary standard " (GB5749-2006) does not also have relevant regulations.But undeniable, for a lot of take underground water as the area of drinking water source, in water, the purification of perchlorate brings challenges to existing water technology.
At present, the perchlorate removal technique of comparative maturity can be divided into Physical, biological process and chemical method.Physical mainly comprises absorption method, ion exchange method and membrane separation process.But Physical just there occurs the transfer or concentrated of pollutent, does not transform thoroughly it.Perchlorate thoroughly can be changed into chlorion by biological process, be widely used at present, its principle is chlorion by the metabolism of microorganism by perchlorate reduction, the difference of carbon source needed for microorganism, can be divided into heterotrophism to remove perchlorate method and autotrophy removes perchlorate method.Heterotrophism removes perchlorate method speed of response soon, and reaction efficiency is high, but sludge growth is comparatively rapid, needs additional organic carbon source simultaneously, easily causes secondary pollution; Autotrophy removes perchlorate using hydrogen as desired electronic donor, is transformed by perchlorate under the condition of inorganic carbon as carbon source, and bacterial multiplication is comparatively slow, and reaction product is comparatively simple, clean, there is not the problem of secondary pollution.But hydrogen also exists inflammable and explosive, not easily transport, the problems such as solubleness is low.It is pointed out that, for biological reducing perchlorate technology, the product that perchlorate is reduced is chlorion, high-concentration chlorine ion is present in the aqueous solution problems such as still can causing the bitter saline taste of water body, salting of soil, corrosive pipeline, plant-growth difficulty.How to realize the deep conversion of perchlorate, be still a technical barrier urgently to be resolved hurrily.
Summary of the invention
The present invention is directed to the perchlorate that general physical and chemical process is difficult to remove, propose perchlorate minimizing technology that a kind of electrochemical process and biological process work in coordination with and relevant reactor, realize the deep conversion of perchlorate-chlorion-reactive chlorine.Instant invention overcomes the defect that biological hydrogen autotrophy removes perchlorate method, by the combination of electrochemistry and biological hydrogen autotrophy process, formed a kind of current efficiency high, simple to operate, be easy to the water body perchlorate removal technology applied in engineering.
Know-why of the present invention is: under the certain current condition of applying, cathode surface generation evolving hydrogen reaction, and the hydrogen of precipitation is utilized by hydrogen autotrophy perchlorate reduction bacterium and by hydrogen autotrophic organism reductive action, the perchlorate in water is converted into chlorion.Then, chlorion is electrochemically oxidized generation reactive chlorine at anode region, and reactive chlorine has germicidal action, can promote effluent quality further, namely realizes the deep conversion of perchlorate → chlorion → reactive chlorine.Said process has given full play to the effect of electrochemistry and microorganism, effectively improves current efficiency, and fully simplifies biological processing unit.
For achieving the above object, the present invention takes following technical scheme:
Perchlorate minimizing technology of the present invention is worked in coordination with in biological removal perchlorate integrated reactor in electrochemistry and is completed.This reactor comprises the unit such as electrode (negative electrode, anode), electrolyzer, direct supply.Direct supply is connected with plain conductor respectively with between negative electrode, anode, and negative electrode, anode are placed in electrolyzer two ends respectively, adopts cationic exchange membrane to be separated by and form cathode zone and anode region between the two poles of the earth.The cathode zone of electrolyzer is also the biochemical reaction zone of microbial process simultaneously, and first the former water by perchlorate contaminated enter cathode zone, then enters anode region until final outflow water, and device is aqueous mode of being back to back; At the perchlorate hydrogen autotrophy reducing bacteria of cathode zone inoculation culture concentration range at 500mg/L-20 000mg/L; The direct current of voltage range between 0.5V-100V is passed at two kinds of electrode two ends, under galvanic effect, cathode generates hydrogen gas, microorganism utilizes electrolytic hydrogen production to be chlorion by perchlorate reduction; Then chlorion is in the oxidized generation reactive chlorine of anode region, thus realizes the deep conversion of perchlorate → chlorion → reactive chlorine.The reactive chlorine produced can carry out further sterilization and disinfection process to water outlet.
The present invention adopts current efficiency higher, and the suitable material of performance is as reactor electrodes.The pole plate that anode adopts any one materials such as nickel plate, titanium plate, ruthenium plate or titanium-ruthenium to make; The pole plate that negative electrode adopts any one materials such as stainless steel plate, iron plate, aluminium sheet, copper coin, graphite cake, carbon fiber sheet, nickel plate, titanium plate or titanium-ruthenium to make.
Foregoing electrolyzer, it is airtight that negative and positive two region can utilize water seal to carry out.Cathode zone can adopt the materials such as gac, hard coal, soft cellulose filler, foam sponge as bio-carrier, and hydrogen autotrophic bacteria adheres on it; Or adopt the form of micro-filtrate membrane filtration that hydrogen autotrophic bacteria is retained in cathode zone.The microbe stuffing of settled organism hydrogen autotrophic bacteria directly contacts with negative electrode, or hydrogen autotrophic bacteria mixed solution directly contacts with negative electrode.
The present invention all can run under underload and high-load condition.For the perchlorate that concentration is lower, apply electric current lower, region, negative and positive the two poles of the earth pH value fluctuating range is little, intakes to enter anode region generation electrochemical oxidation reactions after cathode zone carries out biochemical reaction, then can directly water outlet (as shown in Figure 1); For the perchlorate of high density, apply electric current higher, region, the two poles of the earth pH value fluctuating range is larger, easily microbial biochemical reaction is had an impact, for region, stable negative and positive the two poles of the earth pH value, can adopt the operator scheme of internal recycling, namely the part solution in cathode compartment region can enter anode region after degassed, and the part solution of anode region can enter cathode zone (as shown in Figure 2) after degassed simultaneously.
Perchlorate minimizing technology of the present invention can process the perchlorate contaminated water body lacking organic carbon source, comprises underground water, surface water and industrial sewage.The advantage that the present invention gives prominence to is: current efficiency is high, and speed of response is fast, and biological processing unit simplifies, and easy handling, floor space is little.In addition, reactor of the present invention can organize in parallel use to expand its processing power more.
Accompanying drawing illustrates:
Fig. 1 flow reactor schematic diagram of the present invention (cathode zone adopts biologic packing material fixation of microbe)
Fig. 2 continuous degassing inner circulation reactor of the present invention schematic diagram (cathode zone adopts membrane module to retain microorganism)
Reference numeral:
1 water inlet tank; 2 intake pumps; 3 direct supplys; 4 cationic exchange membranes; 5 negative electrodes; 6 anodes; 7 biologic packing materials; 8 water seals; 9 water outlets; 10 hydrogen autotrophic bacteria mixed solutions; 11 micro-filtration membrane modules; 12 microorganism backflows; 13 degassers; 14 agitators
Embodiment
Embodiment 1:
Reactor cathode compartment effective volume 600mL.Adopt nickel porous plate as negative electrode, titanium ruthenium net, as anode, keeps cathode compartment hydrogen autotrophy perchlorate degraded sludge concentration 5000mg/L, applies electric current 50mA, work as ClO
4 -starting point concentration 10mg/L, during residence time 11h, reactor ClO
4 -clearance > 90%, reactive chlorine transformation efficiency > 95%.
Embodiment 2:
Reactor cathode compartment effective volume 600mL.Adopt stainless steel plate as negative electrode, titanium ruthenium net, as anode, keeps cathode compartment hydrogen autotrophy perchlorate sludge concentration 1000mg/L, applies electric current 100mA, work as ClO
4 -starting point concentration 10mg/L, residence time 8h, reactor ClO
4 -clearance > 95%, reactive chlorine transformation efficiency > 98%, and there is no the accumulation of intermediate product.
Embodiment 3:
Adopt continuous degassing inner circulation reactor, titanium plate is as negative electrode, and titanium ruthenium net is as anode, and reactor cathode compartment effective volume 600mL, cathode compartment hydrogen autotrophy perchlorate degraded sludge concentration 1000mg/L, applies electric current 50mA.Work as ClO
4 -starting point concentration 20mg/L, nitrate recirculation ratio is 0.5, during residence time 16h, reactor ClO
4 -clearance > 95%, reactive chlorine transformation efficiency > 98%, and there is no the accumulation of intermediate product.
Claims (5)
1. an electrochemistry and biological hydrogen autotrophy act synergistically the method for perchlorate in deep conversion water and reactor, it is characterized in that: adopt cationic exchange membrane that DC electrolysis reaction system is divided into negative electrode and anode region, first former water by perchlorate contaminated enter cathode zone, then enter anode region until final outflow water, device is aqueous mode of being back to back; At the perchlorate hydrogen autotrophy reducing bacteria of cathode zone inoculation culture concentration range at 500mg/L-20 000mg/L; Under galvanic effect, cathode generates hydrogen gas, microorganism utilizes electrolytic hydrogen production to be chlorion by perchlorate reduction; Then chlorion is in the oxidized generation reactive chlorine of anode region, namely realizes the deep conversion of perchlorate → chlorion → reactive chlorine.
2. in accordance with the method for claim 1, it is characterized in that cathode zone adopts the materials such as gac, hard coal, soft cellulose filler, foam sponge as bio-carrier, hydrogen autotrophic bacteria adheres on it; Or adopt the form of micro-filtrate membrane filtration that hydrogen autotrophic bacteria is retained in cathode zone.
3. in accordance with the method for claim 1, it is characterized in that electrochemistry is worked in coordination with biological action and is achieved at the direct supply of 0.05-100V by passing to voltage range at electrolyzer negative and positive the two poles of the earth.
4. in accordance with the method for claim 1, it is characterized in that the pole plate that any one materials such as anode employing nickel plate, titanium plate, ruthenium plate or titanium-ruthenium are made; The pole plate that negative electrode adopts any one materials such as stainless steel plate, iron plate, aluminium sheet, copper coin, graphite cake, carbon fiber sheet, nickel plate, titanium plate or titanium-ruthenium to make.
5. in accordance with the method for claim 1, it is characterized in that negative electrode and anode region solution can realize internal recycling after degasser is degassed, namely the solution in cathode compartment region degassed after can enter anode region, simultaneously the solution of anode region degassed after can enter cathode zone, thus 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 |
| CN105253992A (en) * | 2015-11-11 | 2016-01-20 | 河南工业大学 | Method for removing perchlorate in water through electrodialysis ion exchange membrane bioreactor |
| 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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| 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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