CN102249424A - Proton exchange membrane-free microbiological fuel cell sewage treatment system and application method thereof - Google Patents
Proton exchange membrane-free microbiological fuel cell sewage treatment system and application method thereof Download PDFInfo
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- CN102249424A CN102249424A CN2011100841997A CN201110084199A CN102249424A CN 102249424 A CN102249424 A CN 102249424A CN 2011100841997 A CN2011100841997 A CN 2011100841997A CN 201110084199 A CN201110084199 A CN 201110084199A CN 102249424 A CN102249424 A CN 102249424A
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- 239000010865 sewage Substances 0.000 title claims abstract description 66
- 238000011282 treatment Methods 0.000 title claims abstract description 53
- 230000002906 microbiologic effect Effects 0.000 title claims abstract description 20
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 47
- 231100000719 pollutant Toxicity 0.000 claims abstract description 47
- 244000005700 microbiome Species 0.000 claims abstract description 39
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 235000015097 nutrients Nutrition 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 14
- 230000002829 reductive effect Effects 0.000 claims description 13
- 239000001963 growth medium Substances 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 230000000813 microbial effect Effects 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002054 inoculum Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000009629 microbiological culture Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 239000008055 phosphate buffer solution Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000029087 digestion Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011221 initial treatment Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 241000192700 Cyanobacteria Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a proton exchange membrane-free microbiological fuel cell sewage treatment system. The transmission of electrons and protons is facilitated under the coaction of coupling anodic oxidation and cathodic reduction, so that a method for efficiently and simultaneously removing reducible organic pollutants and nitrogen-containing pollutants from sewage is provided. The method comprises the following steps of: domesticating and cultivating microorganisms needed by the removal of pollutants; attaching films to an anode and a cathode of a proton exchange membrane-free microbiological fuel cell respectively; removing reducible organic pollutants under the oxidizing action of anode microorganisms; and transmitting the generated electrons to the cathode through an external circuit connected with an electrode to facilitate the removal of oxidative pollutants with cathode microorganisms.
Description
Technical field
The present invention relates to not have the structure of proton exchange membrane microbiological fuel cell Sewage treatment systems, remove domestication, the cultivation of reductibility organic pollutant and nitrogen-containing pollutant microorganism, specifically a kind of microbiological fuel cell technology of utilizing, strengthen electronics, proton transfer, when promoting in the sewage reductive pollutants and oxidative pollutant, the efficient method of removing.
Background technology
Microbiological fuel cell (Microbial fuel cells, MFCs) be exactly to utilize microorganism to produce the device of electric current as the catalyst oxidation organism, give anode in the electron transport that the positive column oxidation of organic compounds produces, lead through being connected with resistance or load flows to negative electrode, passes to the electron acceptor(EA) in cathodic area again.The MFCs technology have reaction conditions gentleness, substrate extensively, remarkable advantages such as clean and effective and electricity generation performance, be considered to very potential sewage disposal technology.But present most of MFCs only utilizes anodic oxidation separately, and the effect of negative electrode is just for consume electrons and proton, for electronics, the proton transfer of total system provides path, select for use oxygen, the Tripotassium iron hexacyanide and potassium permanganate etc. to have the material of high oxidation reduction potential usually as the cathode electronics acceptor.For the electron acceptor(EA) that prevents negative electrode enters into anode, reduce the anodic reaction efficiency, the normal employing costs an arm and a leg and very easily contaminated proton exchange membrane separation anolyte compartment and cathode compartment, and this has limited the application of MFCs to a great extent.
At present, municipal sewage plant's quantity constantly increases, and wastewater treatment rate also improves constantly, but water body " eutrophication " problem is not well solved, and every year all can occur blue-green algae large-scale outbreak phenomenon as China Taihu Lake in recent years, Dian Chi.This mainly is that the removal of total nitrogen is lower, the ammonia nitrogen (NH of quite a few because prior biological denitride technology energy consumption is big, efficient is low
4 +-N) just change into nitrate nitrogen (NO
3 -N), and fundamentally do not remove.Serious day by day along with the body eutrophication problem, sewage work's sewage drainage standard will improve gradually, and prior biological denitride technology poor processing effect, running cost height, be difficult to realize the qualified discharge of nitrogen-containing pollutant.
Contain a large amount of reductibility organic pollutants (as the COD pollutant) and oxidative pollutant (NO in the city domestic sewage simultaneously
3 --N pollutant), if can make up the MFCs Sewage treatment systems of no proton exchange membrane, the anodic oxidation reductive pollutants, negative electrode is removed oxidative pollutant, realize simultaneously, efficiently removing reductibility organic pollutant and oxidative pollutant in the sewage, this is to improving the domestic sewage treating effect, reducing processing cost, and the aspects such as actual use value that improve MFCs all have very important significance.
Summary of the invention
The invention reside in the ultimate principle of utilizing MFCs provides a kind of while, efficiently removes the method for reductive pollutants and oxidative pollutant in the sewage.Material with easy conductive is an electrode, make up the MFCs Sewage treatment systems of no proton exchange membrane, the microorganism that reductibility organic pollutant and oxidisability nitrogen-containing pollutant are removed in domestication, cultivation, adhere to film forming at anode and negative electrode respectively, coupling anodic oxidation and cathodic reduction effect, promote proton, electron transport, realize simultaneously, efficiently removing reductive pollutants and oxidative pollutant in the sewage.For the efficient removal of reductive pollutants in the municipal effluent and oxidative pollutant provides a kind of effective means.
To achieve these goals, the present invention has made up a kind of MFCs Sewage treatment systems, by electrode, electrode vessel, magnetic stirring apparatus, treatment sewage, outer meeting resistance, compositions such as peristaltic pump, the material that wherein adopts easy conductive is as electrode, electrode places electrode vessel, the microorganism of removing the reductibility organic pollutant adheres to film forming at anode, the microorganism of removing nitrogen-containing pollutant adheres to film forming at negative electrode, cut apart anolyte compartment and cathode compartment without proton exchange membrane, the mobile proton transfer of carrying out by sewage, by lead the two poles of the earth are connected on the external resistance, constitute the loop, strengthen mass transfer process by liquid-flow in the stirring action accelerating system of magnetic stirring apparatus.
MFCs Sewage treatment systems provided by the invention is divided into single chamber type structure and two-chamber-type structure.Wherein, the single chamber type structure is to inoculate microorganism of removing the reductibility organic pollutant and the microorganism of removing nitrogen-containing pollutant respectively in anolyte compartment that is separated from each other and cathode compartment, microorganism is after adhering to film forming on the electrode, two electrode vessels connections are made it to become an electrode vessel, or the two poles of the earth are placed in the same electrode vessel.The two-chamber-type structure is to inoculate microorganism of removing the reductibility organic pollutant and the microorganism of removing nitrogen-containing pollutant respectively in anolyte compartment that is separated from each other and cathode compartment, microorganism is after adhering to film forming on the electrode, by hose connection anolyte compartment and cathode compartment, make treatment sewage obtain circulation, flow.
MFCs Sewage treatment systems provided by the invention when reductibility and oxidative pollutant, is achieved through the following technical solutions in removing sewage:
(1) makes up a kind of MFCs Sewage treatment systems of not having proton exchange membrane, form by electrode, electrode vessel, magnetic stirring apparatus, treatment sewage, outer meeting resistance, peristaltic pump etc., the material that wherein adopts easy conductive is as electrode, electrode places electrode vessel, by lead the two poles of the earth are connected on the external resistance, constitute the loop, strengthen mass transfer process by liquid-flow in the stirring action accelerating system of magnetic stirring apparatus.
(2) preparation is removed reductibility organic pollutant microbiological culture media and is removed the nitrogen-containing pollutant microbiological culture media respectively, and the prescription of wherein removing reductibility organic pollutant microbiological culture media is: (NH
4)
2SO
430mg/L, KH
2PO
430mg/L, KHCO
3500mg/L, MgSO
4200mg/L, FeCl
3100mg/L, CaCl
230mg/L, C
6H
12O
6500mg/L, NaNO
340mg/L; The prescription of removing the nitrogen-containing pollutant microbiological culture media is: (NH
4)
2SO
460mg/L, KH
2PO
430mg/L, KHCO
3500mg/L, MgSO
4200mg/L, FeCl
3100mg/L, CaCl
230mg/L, C
6H
12O
6200mg/L, NaNO
3200mg/L; Every liter of substratum adds liquid microelement 1～2ml, micro-liquid formula: EDTA50.0g/L; ZnSO
42.2g/L; CaCl
25.5g/L; MnCl
24H
2O5.06g/L; FeSO
47H
2O5.0g/L; (NH
4)
6Mo
7O
24H
2O1.1g/L; CuSO
45H
2O1.57g/L; CoCl
26H
2O1.61g/L.
(3) get the sludge seeding in sewage work's second pond or denitrification pond in the nutrient solution of above-mentioned (2), remove domestication, the cultivation of reductibility organic pollutant and nitrogen-containing pollutant desired microorganisms respectively, the pH of control nutrient solution is between 6.5～7.5, when the concentration of microorganism reaches 3000～4000mg/L, and C in the nutrient solution
6H
12O
6And NaNO
3When clearance keeps stablizing, show that microorganism tamed.
(4) microbial suspension that inoculation domestication is good (inoculum size be battery volume 20～30%) is in the MFCs Sewage treatment systems of no proton exchange membrane, the microbial inoculant of removing the reductibility organic pollutant is to the anolyte compartment, the microbial inoculant of removing nitrogen-containing pollutant is to cathode compartment, this moment, anolyte compartment and cathode compartment were independent, separately, with the mud that prevents positive column when adhering to film forming at cathode filming, cathodic area mud is in the anode film forming, thereby influence the wastewater treatment efficiency of system, make microorganism after electrode surface adheres to the formation microbial film, be communicated with anolyte compartment and cathode compartment (can form single chamber type and two-chamber-type treatment system), the external circuit of connection electrode is to resistance, and the entire treatment system constitutes a complete electronics, the proton transfer path.
(5) behind pH regulator to 7 ± 0.2 with treatment sewage, add the phosphate buffer solution of pH=7, the amount of the phosphate buffer solution that is added is 10% of a cumulative volume, and discharge oxygen in the closed system with high pure nitrogen, the treatment sewage that will add phosphoric acid buffer then feeds (1) described MFCs as conductive soln, make anode and negative electrode carry out proton transfer by drainage flow, by controlling the treatment effect that suitable hydraulic detention time reaches to be needed, and the circulation of adopting treatment solution in the stirring method strengthening system is to promote mass transfer process.
(6) adopt volt ohm-milliammeter to measure the open circuit voltage at battery two ends, the content of reductive organic matter (content with COD is represented), ammonia-state nitrogen, nitrite nitrogen and the nitrate nitrogen for the treatment of water effluent liquid is carried out the sewage disposal of analysis and evaluation system.
Of the present invention have following characteristics:
1, do not use proton exchange membrane to cut apart anolyte compartment and cathode compartment, greatly reduce use cost and the use range of MFCs.The microorganism of removing the reductibility organic pollutant adheres to film forming at anode, and the microorganism of removing nitrogen-containing pollutant adheres to film forming at negative electrode.The reductibility organic pollutant is oxidized at anode, and the electronics of generation carries out reduction reaction through the oxidative pollutant that external circuit passes to negative electrode, constitutes the MFCs Sewage treatment systems of no proton exchange membrane.Coupling anodic oxidation and cathodic reduction effect are worked in coordination with, are efficiently removed reductive pollutants in the sewage and oxidisability pollution, have significantly reduced its use cost, have improved its practice in sewage disposal and have been worth
The main difference of substratum of the microorganism of 2, domestication, cultivation removal reductibility organic pollutant and oxidisability nitrogen-containing pollutant is on the content of reductive organic matter, ammonia nitrogen and nitrate nitrogen, and remaining nutritive element is all the same with culture condition, this makes that battery system two kinds of microbial growth conditions when being communicated with operation are approximate, has good microorganism consistency; Adhere to film forming at anode and negative electrode respectively by domestication, cultured microorganism, at anodic microbiological anaerobic digestion organic pollutant, at the microorganism denitrification denitrogenation of negative electrode.
3, the MFCs Sewage treatment systems of no proton exchange membrane, the material that adopts easy conductive is as electrode, adhere to film forming microbiological oxidation at anode and remove reductive pollutants, the electronics that produces promotes the microorganism of negative electrode to carry out denitrification denitrogenation, coupling anodic oxidation and cathodic reduction two processes, and strengthen mass transfer process by stirring action, when realizing in the sewage reductive pollutants and oxidative pollutant, the efficient removal; This structure MFCs Sewage treatment systems does not need expensive proton exchange membrane as separating materials, and the two poles of the earth are utilized simultaneously, and the practice that has significantly improved the MFCs system is worth.
Description of drawings
Fig. 1 does not have the microbiological fuel cell Sewage treatment systems of proton exchange membrane for two-chamber-type of the present invention, wherein 1, fluid-tight, 2, the anolyte compartment, 3, cathode compartment, 4, magnetic stirring apparatus, 5, peristaltic pump, 6, outer meeting resistance, wherein arrow is depicted as the drainage flow direction.
Fig. 2 does not have the microbiological fuel cell Sewage treatment systems of proton exchange membrane for single chamber type of the present invention, wherein 1, anode, and 2, negative electrode, 3, magnetic stirring apparatus, 4, electrode vessel, 5, outer meeting resistance, 6, fluid-tight.
Fig. 3 is the removal efficient of two-chamber-type treatment system to COD pollutant and nitrate nitrogen.
Fig. 4 is the removal efficient of single chamber type treatment system to COD pollutant and nitrate nitrogen.
Embodiment
Embodiment 1: not having proton exchange membrane MFCs Sewage treatment systems treatment of simulated municipal effluent with two-chamber-type is that example further specifies the present invention.
(1) domestication, the cultivation of anaerobically digested sludge and denitrification mud
Anaerobic digestion bacterium culture medium prescription (mg/L): (NH
4)
2SO
430, KH
2PO
430, KHCO
3500, MgSO
4200, FeCl
3100, CaCl
230, C
6H
12O
6500, NaNO
340; Denitrifying bacteria culture medium prescription (mg/L): (NH
4)
2SO
460, KH
2PO
430, KHCO
3500, MgSO
4200, FeCl
3100, CaCl
230, C
6H
12O
6200, NaNO
3200.Every liter of substratum adds liquid microelement 1～2ml, micro-liquid formula (g/L): EDTA50.0; ZnSO
42.2; CaCl
25.5; MnCl
24H
2O5.06; FeSO
47H
2O5.0; (NH
4)
6Mo
7O
24H
2O1.1; CuSO
45H
2O1.57; CoCl
26H
2O1.61.
The sludge seeding of getting sewage work's second pond or denitrification pond is in above-mentioned nutrient solution, carry out domestication, the cultivation of anaerobically digested sludge (bacterium) and denitrification mud (bacterium) respectively, the pH of control nutrient solution is between 6.5～7.5, when the concentration of mud reaches 3000～4000mg/L, and C in the nutrient solution
6H
12O
6(representing the reductibility organic pollutant) and NaNO
3When (representing the oxidisability nitrogen-containing pollutant) clearance keeps stablizing, show that microorganism tamed.
(2) two-chamber-type does not have the structure of the MFCs Sewage treatment systems of proton exchange membrane
Anolyte compartment and cathode compartment all are cylindrical synthetic glass, internal diameter 6cm, and high 10cm, two ends adopt nut to add a cover fixing.Electrode is 80 purpose stainless (steel) wires (45mm * 50mm), use the sulphuric acid soln of lmol/L to soak about 30s, the greasy dirt on flush away surface and impurity etc. before using earlier.The sludge suspension liquid that inoculation domestication is good (inoculum size be battery volume 20～30%) to anolyte compartment and cathode compartment (at this moment respectively, anolyte compartment and cathode compartment are independent of each other), bottom magnetic stirring apparatus stirring at low speed (100rpm), adhered to even, firm microbial film Deng electrode surface, wash out with nutrient solution and to adhere to not firm mud, with flexible pipe anolyte compartment and cathode compartment are linked together, constituting two-chamber-type Sewage treatment systems (as accompanying drawing 2) outer meeting resistance is 1000 Europe.
(3) analysis of wastewater treatment efficiency, investigation
Adopt the deionized water preparation to handle waste water (mg/L): KH
2PO
430, KHCO
3500, MgSO
4200, CaCl
230, NaNO
3200, (NH
4)
2SO
460, FeCl
3100, C
6H
12O
6500, the pH that regulates waste water is 7, adds the phosphate buffer solution (pH=7) of cumulative volume 10%, and with the oxygen in the high pure nitrogen discharge closed system, the sewage for preparing is fed in the microbiological fuel cell, changes primary treatment liquid every day.Analyze the content of COD and nitrate nitrogen in the water-in and water-out respectively, estimate the sewage treatment capacity of this system, concrete outcome is seen accompanying drawing 3.
Embodiment 2: not having proton exchange membrane MFCs Sewage treatment systems treatment of simulated municipal effluent with single chamber type is that example further specifies the present invention.
(1) domestication, the cultivation of anaerobically digested sludge and denitrification mud
Anaerobic digestion bacterium culture medium prescription (mg/L): (NH
4)
2SO
430, KH
2PO
430, KHCO
3500, MgSO
4200, FeCl
3100, CaCl
230, C
6H
12O
6500, NaNO
340; Denitrifying bacteria culture medium prescription (mg/L): (NH
4)
25O
460, KH
2PO
430, KHCO
3500, MgSO
4200, FeCl
3100, CaCl
230, C
6H
12O
6200, NaNO
3200.Every liter of substratum adds liquid microelement 1～2ml, and micro-liquid formula (g/L): EDTA 50.0; ZnSO
42.2; CaCl
25.5; MnCl
24H
2O 5.06; FeSO
47H
2O 5.0; (NH
4)
6Mo
7O
24H
2O1.1; CuSO
45H
2O1.57; CoCl
26H
2O1.61.
The sludge seeding of getting sewage work's second pond or denitrification pond is in above-mentioned nutrient solution, carry out domestication, the cultivation of anaerobically digested sludge (bacterium) and denitrification mud (bacterium) respectively, the pH of control nutrient solution is between 6.5～7.5, when the concentration of mud reaches 3000～4000mg/L, and C in the nutrient solution
6H
12O
6(representing the reductibility organic pollutant) and NaNO
3When (representing the oxidisability nitrogen-containing pollutant) clearance keeps stablizing, show that microorganism tamed.
(2) single chamber type does not have the structure of the MFCs Sewage treatment systems of proton exchange membrane
Anolyte compartment and cathode compartment all are cylindrical synthetic glass, internal diameter 6cm, and high 10cm, two ends adopt nut to add a cover fixing.Electrode is 80 purpose stainless (steel) wires (45mm * 50mm), use the sulphuric acid soln of 1mol/L to soak about 30s, the greasy dirt on flush away surface and impurity etc. before using earlier.The sludge suspension liquid that inoculation domestication is good (inoculum size be battery volume 20～30%) to anolyte compartment and cathode compartment (at this moment respectively, anolyte compartment and cathode compartment are independent of each other), bottom magnetic stirring apparatus stirring at low speed (100rpm), adhered to evenly Deng electrode surface, firm microbial film, wash out with nutrient solution and to adhere to not firm mud, removing anolyte compartment and cathode compartment does not have the lid of that end of fixed electorde, anolyte compartment and cathode compartment are docking together, make anolyte compartment and cathode compartment connect into an electrode vessel (as accompanying drawing 2) and connect into battery system, outer meeting resistance is 100 Europe.
(3) analysis of wastewater treatment efficiency, investigation
Adopt the deionized water preparation to handle waste water (mg/L): KH
2PO
430, KHCO
3500, MgSO
4200, CaCl
230, NaNO
3200, (NH
4)
2SO
460, FeCl
3100, C
6H
12O
6500, the pH that regulates waste water is 7, adds the phosphate buffer solution (pH=7) of cumulative volume 10%, and with the oxygen in the high pure nitrogen discharge closed system, the sewage for preparing is fed in the microbiological fuel cell, changes primary treatment liquid every day.Analyze the content of COD and nitrate nitrogen in the water-in and water-out respectively, estimate the sewage treatment capacity of this system, concrete outcome is seen accompanying drawing 4.
Claims (4)
1. no proton exchange membrane microbiological fuel cell Sewage treatment systems, it is characterized in that by electrode, electrode vessel, magnetic stirring apparatus, treatment sewage, outer meeting resistance, peristaltic pump is formed, the material that wherein adopts easy conductive is as electrode, electrode places electrode vessel, the microorganism of removing the reductibility organic pollutant adheres to film forming at anode, the microorganism of removing nitrogen-containing pollutant adheres to film forming at negative electrode, cut apart anolyte compartment and cathode compartment without proton exchange membrane, anode and negative electrode are by the mobile proton transfer of carrying out of sewage in the electrode vessel, lead is connected to the two poles of the earth on the external resistance, constitute the loop, and strengthen mass transfer process by liquid-flow in the stirring action accelerating system of magnetic stirring apparatus.
2. a kind of no proton exchange membrane microbiological fuel cell Sewage treatment systems according to claim 1, it is characterized in that the anolyte compartment that is separated from each other and cathode compartment inoculate microorganism of removing the reductibility organic pollutant and the microorganism of removing nitrogen-containing pollutant respectively, microorganism is after adhering to film forming on the electrode, two electrode vessels connections are made it to become an electrode vessel, or the two poles of the earth are placed in the same electrode vessel, be the single chamber type structure.
3. a kind of no proton exchange membrane microbiological fuel cell Sewage treatment systems according to claim 1, it is characterized in that the anolyte compartment that is separated from each other and cathode compartment inoculate microorganism of removing the reductibility organic pollutant and the microorganism of removing nitrogen-containing pollutant respectively, microorganism is after adhering to film forming on the electrode, by hose connection anolyte compartment and cathode compartment, make treatment sewage obtain circulation, flow, be the two-chamber-type structure.
4. the described microbiological fuel cell of claim 1 is removed in the sewage reductibility and is contained the nitrogen pollutant method, it is characterized in that the concrete operations step is as follows:
(1) structure of no proton exchange membrane microbiological fuel cell Sewage treatment systems: form this Sewage treatment systems by electrode, electrode vessel, magnetic stirring apparatus, treatment sewage, outer meeting resistance, peristaltic pump, the material that wherein adopts easy conductive is as electrode, electrode places electrode vessel, by lead the two poles of the earth are connected on the external resistance, constitute the loop, strengthen mass transfer process by liquid-flow in the stirring action accelerating system of magnetic stirring apparatus.
(2) preparation is removed reductibility organic pollutant microbiological culture media and is removed the nitrogen-containing pollutant microbiological culture media respectively, and the prescription of wherein removing reductibility organic pollutant microbiological culture media is: (NH
4)
2SO
430mg/L, KH
2PO
430mg/L, KHCO
3500mg/L, MgSO
4200mg/L, FeCl
3100mg/L, CaCl
230mg/L, C
6H
12O
6500mg/L, NaNO
340mg/L; The prescription of removing the nitrogen-containing pollutant microbiological culture media is: (NH
4)
2SO
460mg/L, KH
2PO
430mg/L, KHCO
3500mg/L, MgSO
4200mg/L, FeCl
3100mg/L, CaCl
230mg/L, C
6H
12O
6200mg/L, NaNO
3200mg/L; Every liter of substratum adds liquid microelement 1～2ml, micro-liquid formula: EDTA50.0g/L; ZnSO
42.2g/L; CaCl
25.5g/L; MnCl
24H
2O5.06g/L; FeSO
47H
2O5.0g/L; (NH
4)
6Mo
7O
24H
2O1.1g/L; CuSO
4.5H
2O1.57g/L; CoCl
26H
2O1.61g/L.
(3) get the sludge seeding in sewage work's second pond or denitrification pond in the nutrient solution of above-mentioned (2), remove domestication, the cultivation of reductibility organic pollutant and nitrogen-containing pollutant desired microorganisms respectively, the pH of control nutrient solution is between 6.5～7.5, when the concentration of microorganism reaches 3000～4000mg/L, and C in the nutrient solution
6H
12O
6And NaNO
3When clearance keeps stablizing, show that microorganism tames.
(4) microbial suspension that the inoculation domestication is good is in the microbiological fuel cell Sewage treatment systems of no proton exchange membrane, inoculum size is 20～30% of a battery volume, the microbial inoculant of removing the reductibility organic pollutant is to anode, the microbial inoculant of removing nitrogen-containing pollutant is to negative electrode, anolyte compartment and cathode compartment were independently, separated this moment, make microorganism after electrode surface adheres to the formation microbial film, can constitute single chamber type and two-chamber-type Sewage treatment systems respectively, the external circuit of connection electrode is connected on the resistance;
(5) behind pH regulator to 7 ± 0.2 with treatment sewage, add the phosphate buffer solution of pH=7, the amount of the phosphate buffer solution that is added is 10% of a cumulative volume, and discharge oxygen in the closed system with high pure nitrogen, the treatment sewage that will add phosphoric acid buffer feeds the microbiological fuel cell Sewage treatment systems of (1) described no proton exchange membrane as conductive soln, make anode and negative electrode carry out proton transfer by conductive soln, realize the treatment effect that need reach by the control hydraulic detention time, and the circulation of adopting treatment solution in the stirring method strengthening system is to promote mass transfer process.
(6) adopt volt ohm-milliammeter to measure the open circuit voltage at battery two ends, the content of reductive organic matter, ammonia-state nitrogen, nitrite nitrogen and the nitrate nitrogen for the treatment of water effluent liquid is carried out the wastewater treatment efficiency of this system of assay, and wherein reductive organic matter is represented with COD content.
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| CN106876760A (en) * | 2017-01-22 | 2017-06-20 | 南通大学 | An expandable continuous flow membraneless air cathode microbial fuel cell device |
| CN107377608A (en) * | 2017-07-18 | 2017-11-24 | 常州大学 | It is a kind of efficiently to remove Cr in acid soil6+Microbial fuel cell unit and method |
| CN108195901A (en) * | 2017-12-19 | 2018-06-22 | 清华大学 | A kind of method for nitrate early warning in water body |
| CN110451658A (en) * | 2019-07-25 | 2019-11-15 | 中国科学院过程工程研究所 | A kind of device and method based on Deep-Sea Microorganisms processing nitrogenous compound |
| CN110642375A (en) * | 2019-11-05 | 2020-01-03 | 南京大学 | Photocatalysis coupling autotrophic denitrification reactor |
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| CN102765805A (en) * | 2012-08-08 | 2012-11-07 | 大连民族学院 | Filler for sewage treatment, preparation method of filler and sewage treatment method |
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| CN103887552B (en) * | 2014-04-02 | 2015-10-28 | 江苏省城市规划设计研究院 | The membraneless microbiological fuel cell reactor of synchronous nitration and denitrification can be realized |
| CN105810984A (en) * | 2016-04-28 | 2016-07-27 | 北京化工大学 | Membrane-less microbial fuel cell electrode device capable of combining wastewater treatment process |
| CN106876760B (en) * | 2017-01-22 | 2019-05-03 | 南通大学 | A scalable continuous flow membraneless air cathode microbial fuel cell device |
| CN106876760A (en) * | 2017-01-22 | 2017-06-20 | 南通大学 | An expandable continuous flow membraneless air cathode microbial fuel cell device |
| CN107377608A (en) * | 2017-07-18 | 2017-11-24 | 常州大学 | It is a kind of efficiently to remove Cr in acid soil6+Microbial fuel cell unit and method |
| CN108195901A (en) * | 2017-12-19 | 2018-06-22 | 清华大学 | A kind of method for nitrate early warning in water body |
| CN108195901B (en) * | 2017-12-19 | 2020-05-05 | 清华大学 | A kind of method for early warning of nitrate in water body |
| CN110451658A (en) * | 2019-07-25 | 2019-11-15 | 中国科学院过程工程研究所 | A kind of device and method based on Deep-Sea Microorganisms processing nitrogenous compound |
| CN110642375A (en) * | 2019-11-05 | 2020-01-03 | 南京大学 | Photocatalysis coupling autotrophic denitrification reactor |
| CN117730061A (en) * | 2021-06-08 | 2024-03-19 | 扎森器具切割和定型塑胶中心有限公司 | Apparatus and method for converting ammonia from ammonia-containing aqueous liquid to molecular nitrogen |
| EP4313876B1 (en) * | 2021-06-08 | 2024-07-03 | Jassen - Kunststoffzentrum GmbH - Apparatebau, Zuschnitte und Formung | Apparatus and process for converting ammonia from an ammonia-containing aqueous solution to molecular nitrogen |
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Application publication date: 20111123 |