CN104591401B - An a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon - Google Patents
An a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon Download PDFInfo
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Abstract
An a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon, it relates to a kind of method building and processing ammonia nitrogen waste water of microorganism electrochemical system.It is an object of the invention to, for solving the modes such as existing removal of carbon and nitrogen microorganism electrochemical system many employings negative electrode aeration, adverse current, cause energy consumption big and the uppity problem of dissolved oxygen content.The present invention adopts a filter formula water distribution nozzle that the anode water outlet of reactor is imported to negative electrode, and spills from cathode top cloth, makes air enter device along with water distribution process, and the nitrifier for reactor upper end carries out nitration reaction；Utilizing the dissolved oxygen gradient that reactor cathode chamber is formed in vertical direction, in the nitration reaction that is partially completed on cathode chamber, and the lower part on cathode chamber completes anti-nitration reaction.It is an advantage of the current invention that negative electrode is without aeration, saves energy consumption；Without accurately controlling dissolved oxygen concentration, reduce the complexity of this technique.
Description
Technical field
The present invention relates to a kind of filter formula biological-cathode microbiological electro-chemical systems.
Background technology
Pollutant in waste water are mainly COD and ammonia nitrogen, commonly used along with the high speed development of modern industry and fertilizer and pesticide, and in waste water, ammonia-nitrogen content is continuously increased, and the impact of environment is also caused the concern widely of people by gradually.Its most prominent harm is murder by poisoning aquatile, consumes oxygen, causes body eutrophication and affect the efficiency of chlorination, and what therefore economical and effective dropped reduces ammonia-nitrogen content in waste water has become the key subjects that current environmentalist faces.Relative to physico-chemical process denitrogenation technology, traditional biological denitrogenation technology (nitrated/denitrification) and in the last few years some emerging denitrogenation technology (short-cut nitrification and denitrification, Anammox, whole process autotrophic denitrification etc.) are considered as current most economical effective denitrogenation method because having the advantages such as efficiency height, operating cost is relatively low.But there is also certain problem: a. anaerobic ammonia oxidizing bacteria doubling time length (11d), cause that the reactor start-up time is longer, laboratory it is generally required to 3-6 month, and engineer applied to start the time longer；B. anaerobic ammonia oxidizing bacteria impact resistance is weak, causes the problems such as Full Autotrophic Ammonium Removal Process exists nitrogen load and clearance is low, fluctuation of service；C. for ensureing being smoothed out of denitrification process, carbon source need to additionally be added；D. aeration needs to consume certain energy.
Microorganism electrochemical system is the catalytic action of a kind of available microorganism, is the device of electric energy by the chemical energy in Organic substance.Because it has efficient degradation organic pollution, produces the plurality of advantages such as clean energy resource electric energy, sludge yield are low, of great interest in environment, the energy and field of waste water treatment, and provide a new thinking for bio-denitrification technology.Research finds that biological-cathode type microorganism electrochemical system has the ability of denitrogenation, structure in conjunction with microorganism electrochemical system and traditional biological denitrification reactor, devise the microorganism electrochemical system with denitrification functions of different structure at present, two big class, i.e. single-chamber microbial electro-chemical systems and double-chamber microbiological electro-chemical systems are mainly had according to the difference of configuration.The reaction mechanism of both configurations is identical, namely Organic substance is in anode generation oxidation reaction, the electronics produced is delivered to negative electrode from anode by external circuit, negative electrode generation simultaneous nitrification-denitrification effect, electronic section needed for denitrification process can directly obtain from negative electrode, the electronics produced in the available carbon metabolism process of part.Compared with traditional and emerging biological denitrification process, it is achieved that electric energy can be produced and can remove again the dual-use function of carbon nitrogen, and without additional carbon (the available cathode electronics of denitrifying bacterium is as direct electron donor).And in microorganism electrochemical removal of carbon and nitrogen system, the participation of anaerobic ammonia oxidizing bacteria, is not therefore absent from the problems such as reactor start-up time length, fluctuation of service.Although microorganism electrochemical removal of carbon and nitrogen system is through constantly optimization and improves, having overcome a lot of deficiency, as developed into present integral type synchronous nitration and denitrification microorganism electrochemical system from the initial external nitrification tank of stagewise, the output of system improves constantly, nitrogen processes load and nitrogen removal efficiency significantly improves.But from current reactor design and the application angle that maximizes, there is also following problem: the mode of a. negative electrode many employings adverse current or directly aeration is to realize Nitrification, and this runs counter to the original intention that microorganism electrochemical system recovers energy；B. owing to nitrification and denitrification reaction simultaneously occurs in a space, and the two is completely different to the demand of oxygen, the more difficult c. of control of negative electrode aeration rate exports for the power improving system, negative electrode many employings platinum carbon cathode, which not only improves the construction cost of reactor, more limit its application of maximizing.
Summary of the invention
The present invention is to solve above-mentioned Problems existing, and provides an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon.
A kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon of the present invention, it includes supporting base and reactor casing；Wherein, reactor casing is divided into anode region and cathode chamber two parts；
Described anode region is to be made up of threeway water inlet, anolyte, porous water dispensing board, water guide mouth, aqueduct, oxidation-reduction electrode insert port, titanium silk 1 and two carbon fiber brush anodes；
Described cathode chamber is divided into aerobic section and anoxia section；Described cathode chamber is to be made up of catholyte, outlet, sample tap, temperature sensor insert port, reference electrode insert port, two negative electrodes, titanium silk 2 and refluxing opening；
Wherein, support base is arranged at reactor box bottom, and described anode region is positioned at the bottom of reactor casing, and cathode chamber is positioned at the top of reactor casing, anode region and cathode chamber and is connected by flanged plate；Described flanged plate is fixed with cation exchange membrane, anolyte and catholyte are separated by flanged plate, anolyte is pumped into anode region by the configured threeway water inlet in reactor casing bottom of pump and the porous water dispensing board being arranged on reactor casing inner bottom part, anode region water outlet is flowed out via the water guide mouth on the reactor casing right side wall being arranged on anode region, entering into cathode chamber via aqueduct, the water inlet of described aqueduct connects with the outlet of water guide mouth；Two described carbon fiber brush anodes are placed in anolyte, and are connected with titanium silk 1 respectively；Described titanium silk 1 is arranged at middle and upper part, anode region and extends transversely through and be provided with oxidation-reduction electrode insert port on reactor casing, the reactor casing left side wall between titanium silk 1 and porous water dispensing board；
Described titanium silk 2 is arranged at top, cathode chamber and extends transversely through in reactor casing, and anode region water outlet enters a filter formula water distribution nozzle through aqueduct and is distributed in cathode chamber, forms catholyte；The described outlet dripping filter formula water distribution nozzle water inlet and aqueduct, drip filter formula water distribution nozzle to be fixed on aqueduct bracing frame and be placed in upper end, cathode chamber, described aqueduct bracing frame is screwed on the right side wall of reactor casing, two described negative electrodes are placed in catholyte, article two, negative electrode is connected with titanium silk 2 respectively, being provided with temperature sensor insert port on the reactor casing right side wall on cathode chamber, wall is from top to bottom respectively arranged with reference electrode insert port, sample tap, outlet and refluxing opening to the left；The water side of described outlet connects with the water inlet end of outlet pipe, and the water side of outlet pipe is placed on outlet pipe bracing frame；
Wherein, described titanium silk 1 is connected with load by wire with titanium silk 2.
The present invention is directed to mentioned microorganism electrochemistry removal of carbon and nitrogen system Problems existing, adopt following means to solve the problems referred to above:
A. adopting a filter formula water distribution nozzle that the anode water outlet of reactor is imported to negative electrode, and spill from cathode top cloth, make air enter device along with water distribution process, the nitrifier for reactor upper end carries out nitration reaction, it is not necessary to aeration, saves energy consumption；B. reactor cathode chamber can form dissolved oxygen gradient in vertical direction, utilize this dissolved oxygen concentration gradient, can in the nitration reaction that is partially completed on cathode chamber, and the lower part on cathode chamber completes anti-nitration reaction, without accurately controlling dissolved oxygen concentration, reduce the complexity of this technique；C. adopt carbon fiber brush as biological-cathode, not only reduce system constructing cost but also microorganism adhesion amount can be increased, on negative electrode, part increases cheap stainless (steel) wire roll-in negative electrode to improve the energy output of system simultaneously, increases the probability of its application of maximizing.
The filter formula biological-cathode microbiological electro-chemical systems that drips of the present invention realizes simultaneous denitrification de-carbon process by following principle: rich in Organic substance and ammonia nitrogen (NH4 +-N) waste water from bottom anode region threeway water inlet enter reactor casing, Organic substance in anode region by heterotrophic bacteria decompose release electronics, major part Organic substance be degraded, the ammonia nitrogen (NH of residual organic substances and the overwhelming majority4 +-N) it is incorporated into cathode chamber via aqueduct 11, mainly there is nitration reaction in the aerobic section on cathode chamber, i.e. ammonia nitrogen (NH4 +-N) first under the effect of Nitrosomas, it is converted into nitrite nitrogen (NO2 -N), then nitrite nitrogen (NO under the effect of Nitromonas2 -N) nitrate nitrogen (NO it is converted into3 -N).At the anoxia section on cathode chamber, nitrate nitrogen (NO3 -N) under the effect of denitrifying bacterium, it is converted into N2, complete omnidistance denitrification.In anode region water outlet simultaneously, the Organic substance of residual can be removed further as the electron donor of Denitrification, it addition, the electronics of anode region oxidation operation release can be delivered to negative electrode via external circuit, carries out Denitrification for denitrifying bacterium.
By controlling dissolved oxygen concentration, free ammonia nitrogen (NH4 +-N) concentration, it is possible in a filter formula biological-cathode microbiological electro-chemical systems of this simultaneous denitrification de-carbon, it is achieved short-cut nitrification and denitrification process, to shorten the course of denitrification reaction, to avoid the waste of the energy.As controlled the concentration of dissolved oxygen when below 1mg/L, it is possible to effectively improve nitrite nitrogen (NO2 -N) accumulation, it is suppressed that the growth of Nitromonas；Additionally as free ammonia nitrogen (NH4 +-N) concentration when reaching 150mg/L, it is also possible to significantly inhibit the growth of Nitromonas, thus by ammonia nitrogen (NH4 +-N) oxidation control at nitrite nitrogen (NO2 -N) stage.
The present invention comprises following beneficial effect:
A. ammonia nitrogen (NH4 +-N) create extra proton (H at the Nitrification of cathode chamber aerobic section+), it is possible to consume basicity, reduce negative electrode pH, effectively prevent the negative electrode pH rising phenomenon that electricity generation process causes；
B. the Denitrification that anoxia section in cathode chamber occurs, needed for it, electronics can obtain from external circuit, the removal making nitrogen is no longer subject to the restriction of carbon source as traditional biological denitrification process, solve the tradition nitration denitrification process demand for carbon source thus causing the contradictory problems of competition so that carbon source no longer becomes the limiting factor of removal effect；
C. dripping filter formula water distribution nozzle in the process of water distribution, be brought in catholyte by the oxygen in air, the nitrifier for aerobic section carries out nitration reaction, it is not necessary to aeration, saves energy consumption；
D. cathode chamber can form dissolved oxygen gradient in vertical direction, utilize this dissolved oxygen concentration gradient, nitration reaction can be completed in the upper part (aerobic section) on cathode chamber, and the lower part (anoxia section) on cathode chamber completes anti-nitration reaction, without accurately controlling dissolved oxygen concentration, reduce the complexity of this technique；
E. adopt carbon fiber brush as biological-cathode, not only reduce system constructing cost but also microorganism adhesion amount can be increased, increase cheap stainless (steel) wire roll-in negative electrode to export with the energy improving system in the upper end of cathode chamber aerobic section simultaneously, increase the probability of its application of maximizing.
The present invention relative to prior art advantage be in that following some:
A. compared to traditional removal of carbon and nitrogen reactor, the present invention, while carrying out removal of carbon and nitrogen effect, has electrogenesis function equally.Running (HRT=48h, extrernal resistance 10 Ω) when continuous stream, the outputting current steadily of this system is at about 19.8 ± 1.2mA.
B., while electrogenesis, this system completes the effect of removal of carbon and nitrogen.It is 0.38KgCODm at water inlet organic loading-3d-1,NH4 +-N load is 0.05KgNH4 +-Nm-3d-1When, in a HRT, COD clearance is 88.9 ± 6.7%, and TN clearance is 46.4 ± 2.7%.
C. the Nitrification of negative electrode effectively alleviates electricity generation process and causes the negative electrode pH phenomenon raised, and final outflow water pH is 6.927 ± 0.212, in neutrality.And without in biological-cathode (without buffer) the microorganism electrochemical system of Nitrification, its negative electrode water outlet pH is up to about 9.
Accompanying drawing explanation
Fig. 1 is a filter formula biological-cathode microbiological electro-chemical systems structural representation of the present invention.
Detailed description of the invention
Detailed description of the invention one: a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon of present embodiment, it includes supporting base 1 and reactor casing 2；Wherein, reactor casing 2 is divided into anode region and cathode chamber two parts；
Described anode region is to be made up of threeway water inlet 3, anolyte 4, porous water dispensing board 5, water guide mouth 6, aqueduct 7, oxidation-reduction electrode insert port 17, titanium silk 121 and two carbon fiber brush anodes 20；
Described cathode chamber is divided into aerobic section and anoxia section；Described cathode chamber is to be made up of catholyte 10, outlet 13, sample tap 16, temperature sensor insert port 18,19, two negative electrodes 22 of reference electrode insert port, titanium silk 223 and refluxing opening 26；
Wherein, support base 1 is arranged at bottom reactor casing 2, and described anode region is positioned at the bottom of reactor casing 2, and cathode chamber is positioned at the top of reactor casing 2, anode region and cathode chamber and is connected by flanged plate 12；Described flanged plate 12 is fixed with cation exchange membrane 8, anolyte 4 is pumped into anode region by the configured threeway water inlet 3 in reactor casing 2 bottom of pump 27 with the porous water dispensing board 5 being arranged on reactor casing 2 inner bottom part, anode region water outlet is flowed out via the water guide mouth 6 on reactor casing 2 right side wall being arranged on anode region, entering into cathode chamber via aqueduct 7, the water inlet of described aqueduct 7 connects with the outlet of water guide mouth 6；Two described carbon fiber brush anodes 20 are placed in anolyte 4, and are connected with titanium silk 121 respectively；Described titanium silk 121 is arranged at middle and upper part, anode region and extends transversely through and be provided with oxidation-reduction electrode insert port 17 on reactor casing 2, reactor casing 2 left side wall between titanium silk 121 and porous water dispensing board 5；
Described titanium silk 223 is arranged at top, cathode chamber and extends transversely through in reactor casing 2, and anode region water outlet enters a filter formula water distribution nozzle 9 through aqueduct 7 and is distributed in cathode chamber, forms catholyte 10；The described outlet dripping filter formula water distribution nozzle 9 water inlet and aqueduct 7, drip filter formula water distribution nozzle 9 to be fixed on aqueduct bracing frame 11 and be placed in upper end, cathode chamber, described aqueduct bracing frame 11 is fixed on the right side wall of reactor casing 2 by screw 12, two described negative electrodes 22 are placed in catholyte 10, article two, negative electrode 22 is connected with titanium silk 223 respectively, reactor casing 2 right side wall on cathode chamber is provided with temperature sensor insert port 18, wall is from top to bottom respectively arranged with reference electrode insert port 19 to the left, sample tap 16, outlet 13 and refluxing opening 26；The water side of described outlet 13 connects with the water inlet end of outlet pipe 14, and the water side of outlet pipe 14 is placed on outlet pipe bracing frame 15；
Wherein, described titanium silk 121 is connected with load 25 by wire 24 with titanium silk 223.
The filter formula biological-cathode microbiological electro-chemical systems that drips of present embodiment realizes simultaneous denitrification de-carbon process by following principle: rich in Organic substance and ammonia nitrogen (NH4 +-N) waste water enter reactor casing 2 from the threeway water inlet 3 bottom anode region, Organic substance in anode region by heterotrophic bacteria decompose release electronics, major part Organic substance be degraded, the ammonia nitrogen (NH of residual organic substances and the overwhelming majority4 +-N) it is incorporated into cathode chamber via aqueduct 11, mainly there is nitration reaction in the aerobic section on cathode chamber, i.e. ammonia nitrogen (NH4 +-N) first under the effect of Nitrosomas, it is converted into nitrite nitrogen (NO2 -N), then nitrite nitrogen (NO under the effect of Nitromonas2 -N) nitrate nitrogen (NO it is converted into3 -N).At the anoxia section on cathode chamber, nitrate nitrogen (NO3 -N) under the effect of denitrifying bacterium, it is converted into N2, complete omnidistance denitrification.In anode region water outlet simultaneously, the Organic substance of residual can be removed further as the electron donor of Denitrification, it addition, the electronics of anode region oxidation operation release can be delivered to negative electrode 22 via external circuit, carries out Denitrification for denitrifying bacterium.
By controlling dissolved oxygen concentration, free ammonia nitrogen (NH4 +-N) concentration, it is possible in a filter formula biological-cathode microbiological electro-chemical systems of this simultaneous denitrification de-carbon, it is achieved short-cut nitrification and denitrification process, to shorten the course of denitrification reaction, to avoid the waste of the energy.As controlled the concentration of dissolved oxygen when below 1mg/L, it is possible to effectively improve nitrite nitrogen (NO2 -N) accumulation, it is suppressed that the growth of Nitromonas；Additionally as free ammonia nitrogen (NH4 +-N) concentration when reaching 150mg/L, it is also possible to significantly inhibit the growth of Nitromonas, thus by ammonia nitrogen (NH4 +-N) oxidation control at nitrite nitrogen (NO2 -N) stage.
Present embodiment comprises following beneficial effect:
A. ammonia nitrogen (NH4 +-N) create extra proton (H at the Nitrification of cathode chamber aerobic section+), it is possible to consume basicity, reduce negative electrode pH, effectively prevent the negative electrode pH rising phenomenon that electricity generation process causes；
B. the Denitrification that anoxia section in cathode chamber occurs, needed for it, electronics can obtain from external circuit, the removal making nitrogen is no longer subject to the restriction of carbon source as traditional biological denitrification process, solve the tradition nitration denitrification process demand for carbon source thus causing the contradictory problems of competition so that carbon source no longer becomes the limiting factor of removal effect；
C. dripping filter formula water distribution nozzle 9 in the process of water distribution, be brought in catholyte 10 by the oxygen in air, the nitrifier for aerobic section carries out nitration reaction, it is not necessary to aeration, saves energy consumption；
D. cathode chamber can form dissolved oxygen gradient in vertical direction, utilize this dissolved oxygen concentration gradient, nitration reaction can be completed in the upper part (aerobic section) on cathode chamber, and the lower part (anoxia section) on cathode chamber completes anti-nitration reaction, without accurately controlling dissolved oxygen concentration, reduce the complexity of this technique；
E. adopt carbon fiber brush as biological-cathode, not only reduce system constructing cost but also microorganism adhesion amount can be increased, increase cheap stainless (steel) wire roll-in negative electrode to export with the energy improving system in the upper end of cathode chamber aerobic section simultaneously, increase the probability of its application of maximizing.
Detailed description of the invention two: present embodiment and detailed description of the invention one are 2～2.5:1 the difference is that the ratio of: anode region with the volume on cathode chamber.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one the difference is that: in cathode chamber the separation of aerobic section and anoxia section according to the dissolved oxygen gradient boundary of catholyte in vertical direction 10 as separation.Other is identical with detailed description of the invention one.
Detailed description of the invention four: present embodiment and detailed description of the invention one the difference is that: negative electrode 22 is to be made up of carbon fiber brush, graphite granule and stainless (steel) wire roll-in negative electrode, wherein carbon fiber brush runs through whole cathode chamber, graphite granule is positioned at the anoxia section part on cathode chamber, and stainless (steel) wire roll-in negative electrode is positioned at the upper end of cathode chamber aerobic section；Described graphite granule dosage is 50% cathode chamber volume.Other is identical with detailed description of the invention one.
The carbon fiber brush of present embodiment runs through whole cathode chamber, is used for being enriched with nitrifying bacteria community and denitrification flora；Graphite granule is positioned at the anoxia section on cathode chamber, for increasing the rich carrying capacity of denitrification flora, simultaneously works as the effect of blocking oxygen transmission, maintenance anoxia section anaerobic condition；Stainless (steel) wire roll-in negative electrode is positioned at the upper end of cathode chamber aerobic section, for strengthening the oxygen reduction reaction on cathode chamber, increases the voltage output of this system.
Detailed description of the invention five: present embodiment and detailed description of the invention one the difference is that: anolyte 4 is the waste water rich in Organic substance and ammonia nitrogen, and the pH of anolyte 4 is 7.0～7.2.Other is identical with detailed description of the invention one.
Detailed description of the invention six: present embodiment and detailed description of the invention one the difference is that: being evenly distributed with circular hole on porous water dispensing board 5, Circularhole diameter is 2mm.Other is identical with detailed description of the invention one.
Detailed description of the invention seven: present embodiment and detailed description of the invention one are be adjusted by dripping the height of filter formula water distribution nozzle 9 the difference is that: catholyte 10 dissolved oxygen content.Other is identical with detailed description of the invention one.
Detailed description of the invention eight: present embodiment and detailed description of the invention one the difference is that: dripping filter formula water distribution nozzle 9 is 7.5cm, 10.5cm or 13.5cm apart from the height of catholyte 10, the concentration of corresponding catholyte surface dissolved oxygen respectively 0.2,0.5 and 0.9mgL-1.Other is identical with detailed description of the invention one.
Present embodiment is fixed on reactor casing 2 by aqueduct bracing frame 11 by screw 12, the height dripping filter formula water distribution nozzle 9 by changing the aqueduct bracing frame 11 of different length to regulate, thus regulating the air capacity being brought into cathode chamber in water distribution process, regulation and control catholyte 10 dissolved oxygen content further, controls the reaction rate of anaerobic zone and anoxic zone.
Detailed description of the invention nine: present embodiment and detailed description of the invention one the difference is that: dripping and be evenly distributed with circular hole on filter formula water distribution nozzle 9, Circularhole diameter is 1mm.Other is identical with detailed description of the invention one.
Dripping of present embodiment is evenly distributed with circular hole on filter formula water distribution nozzle 9, has water distribution uniformity and increases the effect of liquid dissolved oxygen concentration in negative electrode.
Detailed description of the invention ten: present embodiment and detailed description of the invention one are the difference is that: remaining Organic substance after react containing anode region in catholyte 10, not nitrated ammonia nitrogen, the nitrate nitrogen of nitration reaction generation and nitrite nitrogen.Other is identical with detailed description of the invention one.
Beneficial effects of the present invention is verified by following example:
Embodiment one:
The filter formula biological-cathode microbiological electro-chemical systems that drips of the simultaneous denitrification de-carbon of (referring to Fig. 1) the present embodiment comprises with lower component.Including the fixing above cation exchange membrane 8 of the flanged plate 12 on the threeway water inlet 7 supported bottom base 1, reactor casing 2, anode region, cathode chamber, anode region and porous water dispensing board 5, jointed anode district and cathode chamber and flanged plate 12, anode water outlet derived and is uniformly distributed into the water guide mouth 6 of negative electrode, aqueduct 7 and drip filter formula water distribution nozzle 9, the outlet 13 negative electrode final outflow water derived and outlet pipe 14, having additionally included aqueduct bracing frame 11 and the outlet pipe bracing frame 15 of fixation.
In this specific embodiment, anode material is carbon fiber brush anode 20, and cathode material is carbon fiber brush negative electrode 22.
Negative electrode 22 in the present embodiment, except using carbon fiber brush negative electrode, also adds graphite granule in the anoxia section on cathode chamber, both can increase the rich carrying capacity of denitrification flora, plays again the effect of blocking oxygen transmission, maintenance anoxia section anaerobic condition simultaneously.Simultaneously also in the upper end of the aerobic section on cathode chamber, add stainless (steel) wire roll-in negative electrode, for strengthening the redox reaction on cathode chamber, improve the energy output of this system.
Being provided with refluxing opening 26 on reactor casing 2 below the outlet 18 of the present embodiment, part water outlet, for being connected with reflux, is back in reactor casing 2 by threeway water inlet 3 and recycles, carry out removal of carbon and nitrogen effect thoroughly by refluxing opening 26.
Owing to aqueduct bracing frame 11 is fixed on reactor casing 2 by screw 12, the aqueduct bracing frame 11 of different length can be changed by dismantling screw, the height dripping filter formula water distribution nozzle 9 can be regulated, thus regulating the air capacity being brought into cathode chamber in water distribution process, regulation and control catholyte 10 dissolved oxygen content further, controls the reaction rate of anaerobic zone and anoxic zone.Wherein the length of aqueduct bracing frame 11 is 7.5cm, 10.5cm or 13.5cm, the concentration of the catholyte surface dissolved oxygen of its correspondence respectively 0.2,0.5 and 0.9mgL-1。
The composition of the anolyte 4 of the present embodiment is: containing 0.13gKCl, 3.32gNaH in 1L anolyte2PO4·2H2O、10.32gNa2HPO4·12H2O, 0.71g sucrose, 0.41gNH4Cl, Trace Metal solution (1mL) and vitamin solution (1mL)；Wherein the value of the C/N of anolyte 4 is about 8.
When adopting tradition nitration denitrification process to process nitrogenous effluent in the present embodiment, C/N value need to can be only achieved denitrification effect more than 7.In the present embodiment, needed for Denitrification, electronics can obtain from external circuit so that the removal of nitrogen is no longer subject to the restriction of carbon source as traditional biological denitrification process, and therefore the present embodiment can be used for processing the nitrogenous effluent of low C/N.
The system of the present embodiment has the effect that
A. ammonia nitrogen (NH4 +-N) create extra proton (H at the Nitrification of cathode chamber aerobic section+), it is possible to consume basicity, reduce negative electrode pH, effectively prevent the negative electrode pH rising phenomenon that electricity generation process causes；
B. the Denitrification that anoxia section in cathode chamber occurs, needed for it, electronics can obtain from external circuit, the removal making nitrogen is no longer subject to the restriction of carbon source as traditional biological denitrification process, solve the tradition nitration denitrification process demand for carbon source thus causing the contradictory problems of competition so that carbon source no longer becomes the limiting factor of removal effect；
C. dripping filter formula water distribution nozzle (9) in the process of water distribution, be brought into by the oxygen in air in catholyte (10), the nitrifier for aerobic section carries out nitration reaction, it is not necessary to aeration, saves energy consumption；
D. cathode chamber can form dissolved oxygen gradient in vertical direction, utilize this dissolved oxygen concentration gradient, nitration reaction can be completed in the upper part (aerobic section) on cathode chamber, and the lower part (anoxia section) on cathode chamber completes anti-nitration reaction, without accurately controlling dissolved oxygen concentration, reduce the complexity of this technique；
E. adopt carbon fiber brush as biological-cathode, not only reduce system constructing cost but also microorganism adhesion amount can be increased, increase cheap stainless (steel) wire roll-in negative electrode to export with the energy improving system in the upper end of cathode chamber aerobic section simultaneously, increase the probability of its application of maximizing.
The present embodiment relative to prior art advantage be in that following some:
A. compared to traditional removal of carbon and nitrogen reactor, the present invention, while carrying out removal of carbon and nitrogen effect, has electrogenesis function equally.Running (HRT=48h, extrernal resistance 10 Ω) when continuous stream, the outputting current steadily of this system is at about 19.8 ± 1.2mA.
B., while electrogenesis, this system completes the effect of removal of carbon and nitrogen.It is 0.39KgCODm at water inlet organic loading-3d-1,NH4 +-N load is 0.05KgNH4 +-Nm-3d-1When, in a HRT, COD clearance is 88.9 ± 6.7%, and TN clearance is 46.4 ± 2.7%.
C. the Nitrification of negative electrode effectively alleviates electricity generation process and causes the negative electrode pH phenomenon raised, and final outflow water pH is 6.927 ± 0.212, in neutrality.And without in biological-cathode (without buffer) the microorganism electrochemical system of Nitrification, its negative electrode water outlet pH is up to about 9.
Embodiment two
The composition of anolyte 4 used by the present embodiment and embodiment one are different in that: containing sucrose 0.71g, NH in 1L anolyte4Cl0.62g, other is all identical with embodiment one.
The present embodiment is 0.39KgCODm at water inlet organic loading-3d-1,NH4 +-N load is 0.08KgNH4 +-Nm-3d-1, when namely C/N is about 5, in a HRT, COD clearance is 92.9 ± 3.2%, and TN clearance is 63.8 ± 2.1%.
Embodiment three
The composition of anolyte 4 used by the present embodiment and embodiment one are different in that: containing sucrose 0.45g, NH in 1L anolyte4Cl0.62g, other is all identical with embodiment one.
The present embodiment is 0.25KgCODm at water inlet organic loading-3d-1,NH4 +-N load is 0.08KgNH4 +-Nm-3d-1, when namely C/N is about 3, in a HRT, COD clearance is 91.5 ± 4.6%, and TN clearance is 40.2 ± 3.3%.
Present invention is not limited only to the content of the respective embodiments described above, and the combination of one of them or several detailed description of the invention can also realize the purpose of invention equally.
Claims (10)
1. the filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon, it is characterised in that it includes supporting base (1) and reactor casing (2)；Wherein, reactor casing (2) is divided into anode region and cathode chamber two parts；
Described anode region is to be made up of threeway water inlet (3), anolyte (4), porous water dispensing board (5), water guide mouth (6), aqueduct (7), oxidation-reduction electrode insert port (17), titanium silk 1 (21) and two carbon fibers brush anode (20)；
Described cathode chamber is divided into aerobic section and anoxia section；Described cathode chamber is to be made up of catholyte (10), outlet (13), sample tap (16), temperature sensor insert port (18), reference electrode insert port (19), two negative electrodes (22), titanium silk 2 (23) and refluxing opening (26)；
Wherein, support base (1) is arranged at reactor casing (2) bottom, described anode region is positioned at the bottom of reactor casing (2), and cathode chamber is positioned at the top of reactor casing (2), anode region and cathode chamber and is connected by flanged plate；Described flanged plate is fixed with cation exchange membrane (8), anolyte (4) and catholyte (10) are separated by flanged plate, anolyte (4) is by the configured threeway water inlet (3) in reactor casing (2) bottom of pump (27) and is arranged on the porous water dispensing board (5) of reactor casing (2) inner bottom part and is pumped into anode region, anode region water outlet is flowed out via the water guide mouth (6) on reactor casing (2) right side wall being arranged on anode region, cathode chamber is entered into via aqueduct (7), the water inlet of described aqueduct (7) connects with the outlet of water guide mouth (6)；Two described carbon fibers brush anode (20) are placed in anolyte (4), and are connected with titanium silk 1 (21) respectively；Described titanium silk 1 (21) is arranged at middle and upper part, anode region and extends transversely through and be provided with oxidation-reduction electrode insert port (17) on reactor casing (2), reactor casing (2) left side wall between titanium silk 1 (21) and porous water dispensing board (5)；
Described titanium silk 2 (23) is arranged at top, cathode chamber and extends transversely through in reactor casing (2), anode region water outlet enters filter formula water distribution nozzle (9) through aqueduct (7) and is distributed in cathode chamber, forms catholyte (10)；The described outlet dripping filter formula water distribution nozzle (9) water inlet and aqueduct (7), drip filter formula water distribution nozzle (9) to be fixed on aqueduct bracing frame (11) and be placed in upper end, cathode chamber, described aqueduct bracing frame (11) is fixed on the right side wall of reactor casing (2) by screw (12), two described negative electrodes (22) are placed in catholyte (10), article two, negative electrode (22) is connected with titanium silk 2 (23) respectively, reactor casing (2) right side wall on cathode chamber is provided with temperature sensor insert port (18), wall is from top to bottom respectively arranged with reference electrode insert port (19) to the left, sample tap (16), outlet (13) and refluxing opening (26)；The water side of described outlet (13) connects with the water inlet end of outlet pipe (14), and the water side of outlet pipe (14) is placed on outlet pipe bracing frame (15)；
Wherein, described titanium silk 1 (21) is connected with load (25) by wire (24) with titanium silk 2 (23).
2. according to claim 1 a kind of drip filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon, it is characterised in that the ratio of anode region and the volume on cathode chamber is 2～2.5:1.
3. according to claim 1 a kind of for simultaneous denitrification de-carbon drip filter formula biological-cathode microbiological electro-chemical systems, it is characterised in that in cathode chamber the separation of aerobic section and anoxia section according to the dissolved oxygen gradient boundary of catholyte in vertical direction (10) as separation.
4. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 1, it is characterized in that negative electrode (22) is to be made up of carbon fiber brush, graphite granule and stainless (steel) wire roll-in negative electrode, wherein carbon fiber brush runs through whole cathode chamber, graphite granule is positioned at the anoxia section part on cathode chamber, stainless (steel) wire roll-in negative electrode is positioned at the upper end of cathode chamber aerobic section, and described graphite granule dosage is 50% cathode chamber volume.
5. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 1, it is characterised in that anolyte (4) is the waste water rich in Organic substance and ammonia nitrogen, and the pH of anolyte (4) is 7.0～7.2.
6. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 1, it is characterised in that porous water dispensing board is evenly distributed with circular hole on (5), and Circularhole diameter is 2mm.
7. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 1, it is characterised in that catholyte (10) dissolved oxygen content is to be adjusted by the height of filter formula water distribution nozzle (9).
8. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 7, it is characterized in that the height dripping filter formula water distribution nozzle (9) distance catholyte (10) is 7.5cm, 10.5cm or 13.5cm, the concentration of corresponding catholyte surface dissolved oxygen respectively 0.2,0.5 and 0.9mgL-1。
9. an a kind of filter formula biological-cathode microbiological electro-chemical systems for simultaneous denitrification de-carbon according to claim 1, it is characterised in that dripping in filter formula water distribution nozzle (9) and be evenly distributed with circular hole, Circularhole diameter is 1mm.
10. according to claim 1 a kind of for simultaneous denitrification de-carbon drip filter formula biological-cathode microbiological electro-chemical systems, it is characterised in that in catholyte (10) containing anode region reaction after remaining Organic substance, not nitrated ammonia nitrogen, nitration reaction generate nitrate nitrogen and nitrite nitrogen.
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