CN108675444A - A kind of apparatus and method rapidly promoting anthraquinone dye decoloration based on microbiological fuel cell technology - Google Patents
A kind of apparatus and method rapidly promoting anthraquinone dye decoloration based on microbiological fuel cell technology Download PDFInfo
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- CN108675444A CN108675444A CN201810349527.3A CN201810349527A CN108675444A CN 108675444 A CN108675444 A CN 108675444A CN 201810349527 A CN201810349527 A CN 201810349527A CN 108675444 A CN108675444 A CN 108675444A
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- anthraquinone dye
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- fuel cell
- anaerobic sludge
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000001000 anthraquinone dye Substances 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 27
- 230000002906 microbiologic effect Effects 0.000 title claims abstract description 24
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 230000001737 promoting effect Effects 0.000 title claims abstract description 5
- 239000010802 sludge Substances 0.000 claims abstract description 47
- 230000005611 electricity Effects 0.000 claims abstract description 20
- 241000894006 Bacteria Species 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 9
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000010865 sewage Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 239000010439 graphite Substances 0.000 claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 238000005273 aeration Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 238000005276 aerator Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007836 KH2PO4 Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052603 melanterite Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004042 decolorization Methods 0.000 abstract description 11
- 238000004043 dyeing Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 17
- 239000000975 dye Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000010784 textile waste Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 241000863430 Shewanella Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Treatment Of Sludge (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of apparatus and method rapidly promoting anthraquinone dye decoloration based on microbiological fuel cell technology,Belong to technical field of sewage,This method is based on anaerobic sludge decoloration and bioelectrochemistry treatment technology is combined,By building double-chamber microbiological fuel cell system,Electricity production bacterium and the anaerobic sludge with decoloration function is added in anode,And decoloration of the glucose as co-substrate collaboration to anthraquinone dye reactive brilliant bule KN R is added,It is nutriment that culture solution is added simultaneously,Ensure the anaerobic environment of anode,Cathode is passed through electron acceptor of the air as system,Outer connecting resistance constitutes circuit,The quick decolorization of the device of the invention and method for anthraquinone dye has good effect,Also floor space is small,It is applied widely,Equipment is simple,Operation is easy,High treating effect,The advantages that recycling the energy,It can be widely applied to the biological treatment of sewage in dyeing and recovery section electric energy,With good economic efficiency and environmental benefit.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to one kind is rapidly promoted based on microbiological fuel cell technology
The apparatus and method of anthraquinone dye decoloration.
Background technology
Dyeing waste water is the main body of textile waste, and quantity has accounted for 80% or more of textile waste discharge.Print
Dye waste water is the waste water of the processes such as destarch, bleaching, dyeing, printing, arrangement in dyeing process discharge, usually contains dyestuff, washes
The ingredients such as agent, sulfide, solvent, heavy metal and inorganic salts are washed, there is big water, coloration depth, complicated component, environmental pollution
The features such as serious.The energy consumption problem how dyeing waste water is reduced while accomplishing qualified discharge in treatment process is put in ring
One important topic in border scientific and engineering field.It is shown according to Chinese environmental statistical communique in 2013：At 41 of investigation statistics
In industrial trade, the wastewater discharge of textile industry is located at first 4, and textile waste discharge capacity is 21.5 hundred million tons, and textile industry waste water
5 provinces are Zhejiang, Jiangsu, Guangdong, Shandong and Fujian successively before discharge capacity, and 5 province textile industry wastewater discharges are
17.4 hundred million tons, account for the 81.1% of the sector focal investigation industrial enterprise wastewater discharge.And actually at the dyeing waste water in China
Reason Facilities Construction seriously lags, and waste water also fails to complete qualified discharge, and waste water reuse rate is low.
Anthraquinone dye is only second to azo dyes because becoming with stable thick and aromatic ring structure and wide applicability
The second largest reactive dye.The waste water of anthraquinone dye has high coloration, decoloration hardly possible, complicated component, strong toxicity and biodegradability poor
The features such as, method such as the methods of the degradation of activated sludge process, Fenton, absorption of traditional processing anthraquinone dye wastewater are specific
Have feasibility and practicability under situation, but all inevitably cause secondary pollution, and cost is high, it is difficult to adapt to current
The more environmental standard of severization.
The microbiological fuel cell technology (Microbial fuel cells, MFC) to grow up recent years is abundant
The new technology that energy in waste water is combined with electrochemistry, microbiological fuel cell technology are a kind of changes by organic matter
The device of electric energy can be converted by learning, it can obtain electric energy from extensive organic wastewater, be completed at the same time wastewater treatment, rapidly at
For new concept wastewater treatment hot spot, MFC technologies have been obtained for widely verifying in laboratory scale, wherein the anode of MFC
Can not only simple pure compound be utilized to produce electricity, but also electric energy can be directly acquired from complicated organic wastewater, while is complete
At wastewater treatment.The research produced electricity as microbiological fuel cell electron donor using complicated organic matter at present is commonplace, profit
Coverage has been obtained with microbiological fuel cell technology azo dyes reduction-decolor.But it is rare to decolourize to drop to anthraquinone dye
The report of solution.Therefore, it in order to realize the quick decolorization to anthraquinone dye, while recycling electric energy, realizing efficiently using for resource,
Invent it is a kind of using microbiological fuel cell technology with synchronizing of being combined of Anaerobic Microbiological Treatment Technology to anthraquinone dye decoloration and
The apparatus and method of electricity production can expand the new method and new approaches for the treatment of of dyeing wastewater.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art places, for biological treatments such as existing aerobic, anaerobism
The shortcomings of method is slow, the sludge acclimatization period is long to anthraquinone dye decolorization rate provides a kind of based on microbiological fuel cell skill
Art rapidly promotes the apparatus and method of anthraquinone dye decoloration.
One of the technical solution adopted by the present invention to solve the technical problems is：
A method of anthraquinone dye decoloration is promoted based on microbiological fuel cell technology, including：
1) anaerobic sludge is tamed using addition co-substrate and the method for stepping up anthraquinone dye concentration gradient：
Domestication anaerobic sludge culture solution include：2.8~3.2g L-1NaCl, 0.09~0.10g L-1NH4Cl, 0.02~
0.03g L-1 KH2PO4, 1.4~1.6g L-1NaHCO3, 1.5~1.6mg L-1FeSO4, 4.9~5.0mg L-1MnSO4、0.70
~0.75mg L-1ZnSO4, 0.01~0.02mg L-1CaCl2·6H2O, 0.4~0.5mg L-1CuSO4·5H2O, 0.05~
0.15g L-1 CoCl2·6H2O, 0.05~0.15mg L-1MgSO4；And co-substrate and anthraquinone dye；
The culture solution of the anaerobic sludge and the domestication anaerobic sludge is added to anode chamber, and electricity production bacterium is added to cathode
Room；It is 30 ± 2 DEG C, 500~700rpm of speed of agitator to adjust anode room temperature, pH value 7~8, sealing domestication；It waits for contaminating anthraquinone
The decolorization rate of material increases anthraquinone dye concentration after stablizing continues to tame；Wait for anthraquinone of the anaerobic sludge to highest gradient concentration
After the decolorization rate of dyestuff is stablized, the domestication of anaerobic sludge is completed；
2) anaerobic sludge tamed is placed in anode chamber, sodium acetate is added as electron donor, and adds in inoculation electricity production bacterium
Enter the buffer solution of pH values 6.8~7.2 and culture solution fills it up with anode chamber, the slow of identical pH value 6.8~7.2 is added in cathode chamber
Rush solution and culture solution；It is 30 ± 2 DEG C to adjust anode room temperature, 500~700rpm of speed of agitator；Cathode chamber is aerated, and control exposes
Tolerance is 0.5~10L/min, and dissolved oxygen DO is 2.0~6.0mg/L, and at negative and positive the two poles of the earth, external load resistance composition is closed back
Road carries out the domestication of microbiological fuel cell；When voltage rechanges liquid less than 20mV；After voltage stabilization, microorganism is completed
The domestication of fuel cell；
3) anthraquinone dye is added toward the anode chamber of the microbiological fuel cell after domestication, it is 30 ± 2 to adjust anode room temperature
DEG C, 500~700rpm of speed of agitator；Cathode chamber is aerated, and control aeration quantity is 0.5~10L/min, dissolved oxygen DO for 2.0~
6.0mg/L decolourizes to anthraquinone dye.
In one embodiment：The anaerobic sludge is derived from the anaerobism section sludge of Xiamen sewage treatment plant.
In one embodiment：The anthraquinone dye is Reactive Brilliant Blue KN-R；The co-substrate is the Portugal of 0.8~1.2g/L of concentration
Grape sugar.
In one embodiment：In the step 1), anthraquinone dye concentration is gradually incremented to 38~50mg/L from 9~11mg/L.
In one embodiment：In the step 2), buffer solution and the culture solution of pH value 6.8~7.2 include：22~23g/L
Na2HPO4, 5.9~6.0g/L NaH2PO4, 0.8~1.2g/L NaHCO3, 0.05~0.15g/L KCl, 5.8~5.9g/L
NaCl, 0.2~0.3g/L NH4Cl, 0.005~0.015mg/L CaCl2, 1.5~1.6mg/L FeSO4·7H2O、0.005
~0.015mg/L CoCl2·6H2O, 4.9~5.0mg/L MnSO4·H2O, 0.70~0.75mg/L ZnSO4·7H2O、0.4
~0.5mg/L CuSO4·5H2O。
In one embodiment：In the step 2), load resistance is 900~1100 Ω.
The technical solution adopted by the present invention to solve the technical problems second is that：
A kind of device applied to above-mentioned method, described device include anode chamber, cathode chamber and are located at anode chamber and the moon
Amberplex between pole room；The anode chamber is equipped with anode electrode, heating device and agitating device；The cathode chamber is set
There are cathode electrode and aerator；Anode electrode is connected with cathode electrode by external circuit, which is equipped with load electricity
Resistance.
In one embodiment：The anode chamber is additionally provided with anode filling opening, and the cathode chamber is additionally provided with cathode filling opening；It is described
Aerator includes interconnected aerator and aeration head, further includes flow controller；The external circuit is additionally provided with circuit and opens
It closes.
In one embodiment：The material of the anode electrode is graphite felt, carbon paper, carbon cloth, graphite rod or stainless (steel) wire；It is described
The material of cathode electrode is graphite felt, carbon paper, carbon cloth, graphite rod or stainless (steel) wire.
In one embodiment：The graphite felt is to pass through pretreated graphite felt, and the preprocess method is will be without gold
The graphite felt for belonging to modified oxide is placed in the aqueous solution for the hydrogen peroxide that mass fraction is 9~11%, is handled at 85~95 DEG C
Then 1~3h handles 1~3h at the same temperature with water, drying.
Compared with the background art, it has the following advantages that the technical program：
1) present invention promotes anthraquinone dye quick decolorization and recovery section electric energy using microbiological fuel cell technology, effectively
Ground realizes waste water reclaiming；
2) present invention is the further promotion decolourized to anthraquinone dye to traditional anaerobic organism, traditional microbial technique
It is combined with bioelectrochemistry technology；
3) function that electricity production recovers energy not only may be implemented compared to traditional microbiological fuel cell in the present invention, but also
Wastewater treatment may be implemented；
4) anthraquinone dye of the present invention can further promote microorganism as the electron medium of microbiological fuel cell conduction
The output of fuel cell power energy.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is that the embodiment of the present invention uses the decolorization that anthraquinone dye is rapidly promoted based on microbiological fuel cell technology
Device and flow chart.
Fig. 2 is the glucose of various concentration as co-substrate Synergistic degradation reactive brilliant bule design sketch.
It in concentration of glucose is 1g/L that Fig. 3, which is domestication anaerobic sludge, and KN-R concentration is incremented to the de- of 40mg/L from 10mg/L
Color rate figure.
Fig. 4 is that the electricity production design sketch after dyestuff is tamed and be added to microbiological fuel cell.
Fig. 5 is under comparison Aerobic-anaerobic-MFC systems and sterile aeration condition to the degradation effect of reactive brilliant bule and MFC pairs
Reactive brilliant bule degradation UV-VIS figures.
Reference numeral：1, thermometer 2, adding mouth 3, anaerobism anode chamber 4, stirring rotator 5, anode electrode 6, external resistance
7, switch 8, ionic membrane 9, cathode electrode 10, aerator 11, aeration head 12, aerobic cathode chamber 13, silicone tube
Specific implementation mode
Present disclosure is illustrated below by embodiment：
Embodiment 1
Fig. 1 is please referred to, anthraquinone dye decoloration is rapidly promoted based on microbiological fuel cell technology for one kind of the present embodiment
Device, described device includes anode chamber, cathode chamber and the amberplex being located between anode chamber and cathode chamber；The sun
Pole room is equipped with anode filling opening, anode electrode, heating device and agitating device；The cathode chamber is equipped with cathode filling opening, cathode
Electrode and aerator, aerator include the aerator and aeration head being interconnected by silicone tube, which is, for example,
Air compressor, the aeration head are, for example, sand core aeration head, further include flow controller；Anode electrode and cathode electrode pass through
External circuit connects, which is equipped with the load resistance and contactor of 1000 Ω.
The material of anode electrode can be graphite felt, carbon paper, carbon cloth, graphite rod or stainless (steel) wire；The material of cathode electrode
Can be graphite felt, carbon paper, carbon cloth, graphite rod or stainless (steel) wire.Preferably, the material of anode electrode is graphite felt, cathode electricity
The material of pole is graphite felt, conductive energy.
Among the present embodiment, the material of anode electrode and cathode electrode all select it is conductive can, without any
The graphite felt of modified metal oxide, it is highly preferred that being pre-processed according to the following steps to graphite felt：Graphite felt is placed in
Mass fraction be 10% hydrogen peroxide aqueous solution in, at 90 DEG C water-bath boil 2h, be then in same temperature with deionized water
Water-bath is boiled 2 times, each 1h at 90 DEG C, then long 5cm × wide 5cm sizes are cut into after being dried with baking oven, is put on titanium silk, obtain through
Cross pretreated graphite felt anode electrode and graphite felt cathode electrode.
The assemble method of the device of the present embodiment is as follows：
It will be outward pierced by by interior from the shell aperture of anode chamber by the titanium silk of pretreated graphite felt anode electrode, electrode
Plane is parallel with the shell plates plane of anode chamber, is glued the shell aperture of titanium silk and anode chamber with AB glue, places about
10min makes its solidification, will be packed into cathode chamber in the same way by pretreated graphite felt cathode electrode, then by anion
Exchange membrane is pressed on the shell of cathode chamber, is then fixed the shell of cathode chamber, amberplex with the shell of anode chamber,
Screw nut is finally screwed on, anode chamber, cathode chamber and amberplex between the two are fixed, anode electrode, anion are handed over
It changes film and cathode electrode is mutually parallel.Anode chamber and cathode chamber is isolated by amberplex, itself is free on amberplex
Hole can penetrate proton and water.
Embodiment 2
The device of embodiment 1 needs first to carry out sludge acclimatization applied to before dye decolored：
1. sludge acclimatization：
The anaerobism section sludge that the anaerobic sludge that the present invention uses takes for Xiamen sewage treatment plant, using addition co-substrate grape
Sugar and the acclimation method for stepping up anthraquinone dye-Reactive Brilliant Blue KN-R concentration gradient：
The culture formula of liquid for taming anaerobic sludge is as follows：3.0g L-1NaCl、0.095g L-1NH4Cl、0.027g L- 1KH2PO4、 1.5.0g L-1NaHCO3、1.55mg L-1FeSO4、4.95mg L-1MnSO4、0.71mg L-1ZnSO4、0.015mg
L-1 CaCl2·6H2O、0.48mg L-1CuSO4·5H2O、0.1g L-1CoCl2·6H2O、0.1mg L-1MgSO4；And correspondingly
The Reactive Brilliant Blue KN-R (10mg/L~50mg/L) of the glucose and various concentration of various concentration is added.
The acclimation method of anaerobic sludge is as follows：It is carried out in the device of embodiment 1, anaerobic sludge and domestication anaerobic sludge
Culture solution is added to anode chamber, and electricity production bacterium solution (being diluted with distilled water, pH value 7.0) (this of a concentration of 5g/L is added in cathode chamber
The electricity production bacterium that embodiment uses is bought for the mixed cell rich in Shewanella in Chinese Sea Microbiological Culture Collection management
Center, deposit number 1A01328)；Anaerobic sludge is controlled at 30 DEG C, magnetic ion agitator speed in anode chamber
Under the conditions of 600rpm, pH is controlled between 7~8, sealing domestication.It is stepped up in anode chamber during domestication and tames anaerobism
The concentration of reactive brilliant bule in the culture solution of sludge, such as 40mg/L can be incremented to from 10mg/L, 20mg/L, 30mg/L, each
During the domestication of concentration, sludge decolorization rate can continuously decrease, and wait for that sludge decolorization rate within certain time such as 48h is steady
It is fixed, you can to think that concentration domestication is completed, that is, complete an acclimation period, next acclimation period can be carried out, that is, it is gorgeous to increase activity
The supreme concentration gradient of concentration of indigo plant continues to keep the concentration gradient as needed, continues to tame.
Sludge acclimatization result such as Fig. 2 and Fig. 3 in the apparatus and method of the present embodiment add sludge the Portugal of various concentration
The co-substrate that grape sugar is degraded as reactive brilliant bule, wherein concentration of glucose be respectively 0,1,2,3g/L, reactive brilliant bule is a concentration of
40mg/L, and domestication anaerobic sludge culture solution is added, culture domestication under anaerobic, as seen from Figure 2, in glucose
When a concentration of 1g/L, the decolorizing effect of KN-R is best.Experiment among the present embodiment is using addition glucose 1g/L as dyestuff
The co-substrate of degradation.
By taming 4 acclimation periods to anaerobic sludge, decolorizing efficiency is as shown in figure 3, taming and dociling by 4 acclimation periods
Change, the decolorizing efficiency of sludge reaches 83.01%, and sludge acclimatization is completed.
2. the device of the present embodiment starts and as follows specifically for the operating process of anthraquinone dye decoloration：
(1) on device basic after the completion of above-mentioned anaerobic sludge is tamed, liquid in device is discarded, then into anode chamber
The electricity production bacterium solution of a concentration of 5g/L for the anaerobic sludge inoculation 10mL that domestication is completed, is added 20mmol/L sodium acetates as electronics
Donor, the phosphate buffer solution for being 7.0 with pH fill it up with anode chamber with culture solution；It is 30 DEG C to adjust anode room temperature, and stirring turns
600 rpm of speed；Phosphate buffer solution and the culture solution that pH is 7.0 is also added in cathode chamber, and is aerated by aerator, uses gas
Flowmeter body control cathode aeration quantity be 0.5~10L/min, dissolved oxygen DO be 2.0~6.0mg/L, external 1000 Ω resistance,
External multimeter, operation start, and connect data collector gathered data, it is primary that acquisition in 10 minutes is divided between setting gathered data.
When voltage drop (discards liquid in device, rejoin electricity production bacterium, second down to 20mV hereinafter, rechanging liquid culture
Sour sodium, the phosphate buffer solution for being 7.0 with pH fill it up with anode chamber and cathode chamber with culture solution), it changes the liquid once as a week
Phase after running four periods, after cell voltage keeps basicly stable, shows start battery success, stable, completes electricity
The domestication process in pond；
The ingredient of the wherein mixed liquor of the phosphate buffer solution and culture solution of pH 7.0 includes 22.2g/L Na2HPO4、
5.92g/L NaH2PO4、1.0g/L NaHCO3、0.10g/L KCl、5.88g/L NaCl、0.25g/L NH4Cl and mineral
Matter, wherein every liter of content of mineral substances is 0.01mg CaCl2、1.55mg FeSO4·7H2O、0.01mg CoCl2·6H2O、
4.95mg MnSO4·H2O、0.71mg ZnSO4·7H2O、0.48mg CuSO4·5H2O。
By using transformation external resistance method measured power density, respectively 9000 Ω, 6000 Ω, 4000 Ω, 2000 Ω,
One is recorded under 1000 Ω, 800 Ω, 600 Ω, 400 Ω, 200 Ω, 100 Ω, 75 Ω, 50 Ω, 25 Ω resistance respectively completely
MFC intermittent cycles reach maximum burning voltage.
(2) after battery operation is stablized, dye activity brilliant blue KN-R is added in anode chamber, it as needed can appropriate supplement portion
Divide the anaerobic sludge tamed；Sealing plug is used in combination magnetic stirring apparatus controlled at 30 DEG C, and setting rotating speed is 600rpm, cloudy
Pole adds aeration, aeration quantity to be 0.5~10L/min, and dissolved oxygen DO is 2.0~6.0mg/L.It is powered, it is gorgeous to activity to detect the device
The decolorizing effect of blue KN-R.
The apparatus and method of the present embodiment are as shown in Figure 4 in the front and back battery electricity generation performance situation of domestication：By 4 periods
Add its electricity generation performance of the domestication of sodium acetate to tend towards stability, the battery voltage of external 1000 Ω reaches 0.4V, in the period 5 plus
Ltage rate is promoted to 0.4V or more after entering dye activity brilliant blue KN-R, illustrates Reactive Brilliant Blue KN-R as a kind of Problem of Electronic Broker
Body promotes the electricity production of battery.
The apparatus and method of the present embodiment are in the traditional aerobic, anaerobism of comparison and bacteria control decolorizing effect as schemed
Shown in 5, as seen from the figure, with the extension of time, the activity in bacteria control, anaerobism, aerobic and the present embodiment MFC systems
Brilliant blue KN-R declines with the extension of time, and as shown in Figure 5, MFC systems are to the decolorization rate of reactive brilliant bule higher than simple
Anaerobic sludge and aerobic sludge, possible cause is the decoloration that there is electro-chemical activity bacterium can promote dyestuff, the dirt of MFC systems
Mud composition is by anaerobic sludge power-up chemism thalline system, and the generation of electronics further accelerates the decoloration of dyestuff again.By
The degradation of 96h, aerobic, anaerobism, MFC percent of decolourization be respectively 67.86%, 73.08%, 86.27%, wherein sterile aeration
Removal rate is 26.49%.
It follows that the apparatus and method of the present embodiment are better than traditional anaerobism, aerobic body on promoting dye decolored ability
System.
The apparatus and method of the present embodiment are in the traditional aerobic, anaerobism of comparison and bacteria control decolorizing effect and right
Different time degrade water sample carry out UV-vis full wavelength scanners, by aerobic, anaerobism, MFC system water samples with time change
Full spectrum analysis it is found that with the extension of time, reactive brilliant bule the absorption peak of 590nm, 240nm, 310nm occur by
Decrescence weak trend, by consulting literatures it is found that 590nm may be the hydrogen bond action in anthraquinone dye between amino and hydroxyl,
To strengthen the effect between lone electron pair and anthraquinone ring.Weak absorbing band at 310nm is the work of lone electron pair on hydroxyl
With matrix structure-aromatic ring structure of the 240nm absorption bands between anthraquinone dye.Absorption peak is along with water body face at 590nm
Color disappears together, shows that the conjugated structure of KN-R systems is destroyed.Other two absorption band weakens, and shows the broken of aromatic ring structure
It is bad.
It is aerobic, have appearance along with new peak in anaerobic processes, but aerobic weaken at the peak that 240nm goes out with anaerobism
Speed it is slower, still larger in 96h peak areas, water body still shows light blue.And MFC systems 240nm, 310nm with
And the peak of 590nm weakens, to further illustrate that MFC is dye decolored better than traditional anaerobism, aerobic system in promotion.
The above, only present pre-ferred embodiments, therefore cannot limit the scope of implementation of the present invention according to this, i.e., according to
Equivalent changes and modifications made by the scope of the claims of the present invention and description all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of method promoting anthraquinone dye decoloration based on microbiological fuel cell technology, it is characterised in that：Including：
1) anaerobic sludge is tamed using addition co-substrate and the method for stepping up anthraquinone dye concentration gradient：
Domestication anaerobic sludge culture solution include：2.8~3.2g L-1NaCl, 0.09~0.10g L-1NH4Cl, 0.02~0.03g
L-1KH2PO4, 1.4~1.6g L-1NaHCO3, 1.5~1.6mg L-1FeSO4, 4.9~5.0mg L-1MnSO4, 0.70~
0.75mg L-1ZnSO4, 0.01~0.02mg L-1CaCl2·6H2O, 0.4~0.5mg L-1CuSO4·5H2O, 0.05~0.15g
L-1CoCl2·6H2O, 0.05~0.15mg L-1MgSO4；And co-substrate and anthraquinone dye；
The culture solution of the anaerobic sludge and the domestication anaerobic sludge is added to anode chamber, and electricity production bacterium is added to cathode chamber；It adjusts
It is 30 ± 2 DEG C, 500~700rpm of speed of agitator to save anode room temperature, pH value 7~8, sealing domestication；It waits for taking off anthraquinone dye
The concentration for increasing anthraquinone dye after color rate stabilization continues to tame；Wait for anaerobic sludge to the de- of the anthraquinone dye of highest gradient concentration
After color rate stabilization, the domestication of anaerobic sludge is completed；
2) anaerobic sludge tamed is placed in anode chamber, sodium acetate is added as electron donor, and pH is added in inoculation electricity production bacterium
The buffer solution of value 6.8~7.2 fills it up with anode chamber with culture solution, and the buffer solution of identical pH value 6.8~7.2 is added in cathode chamber
With culture solution；It is 30 ± 2 DEG C to adjust anode room temperature, 500~700rpm of speed of agitator；Cathode chamber is aerated, and control aeration quantity is
0.5~10L/min, dissolved oxygen DO are 2.0~6.0mg/L, and at negative and positive the two poles of the earth, external load resistance constitutes closed circuit, carries out micro-
The domestication of biological fuel cell；When voltage rechanges liquid less than 20mV；After voltage stabilization, microbiological fuel cell is completed
Domestication；
3) anthraquinone dye is added toward the anode chamber of the microbiological fuel cell after domestication, it is 30 ± 2 DEG C to adjust anode room temperature, is stirred
500~700rpm of mix rotating speed；Cathode chamber is aerated, and control aeration quantity is 0.5~10L/min, and dissolved oxygen DO is 2.0~6.0mg/L,
It decolourizes to anthraquinone dye.
2. according to the method described in claim 1, it is characterized in that：The anaerobic sludge is derived from the anaerobism of Xiamen sewage treatment plant
Section sludge.
3. according to the method described in claim 1, it is characterized in that：The anthraquinone dye is Reactive Brilliant Blue KN-R；The cobasis
Matter is the glucose of 0.8~1.2g/L of concentration.
4. according to the method described in claim 1, it is characterized in that：In the step 1), anthraquinone dye concentration is from 9~11mg/L
Gradually it is incremented to 38~50mg/L.
5. according to the method described in claim 1, it is characterized in that：In the step 2), the buffer solution of pH value 6.8~7.2
Include with culture solution：22~23g/L Na2HPO4, 5.9~6.0g/L NaH2PO4, 0.8~1.2g/L NaHCO3, 0.05~
0.15g/L KCl, 5.8~5.9g/L NaCl, 0.2~0.3g/L NH4Cl, 0.005~0.015mg/L CaCl2, 1.5~
1.6mg/L FeSO4·7H2O, 0.005~0.015mg/L CoCl2·6H2O, 4.9~5.0mg/L MnSO4·H2O, 0.70~
0.75mg/L ZnSO4·7H2O, 0.4~0.5mg/L CuSO4·5H2O。
6. according to the method described in claim 1, it is characterized in that：In the step 2), load resistance is 900~1100 Ω.
7. a kind of device applied to method according to any one of claims 1 to 6, it is characterised in that：Described device includes
Anode chamber, cathode chamber and the amberplex being located between anode chamber and cathode chamber；The anode chamber is equipped with anode electrode, heating
Device and agitating device；The cathode chamber is equipped with cathode electrode and aerator；Anode electrode and cathode electrode pass through external circuit
Connection, the external circuit are equipped with load resistance.
8. device according to claim 7, it is characterised in that：The anode chamber is additionally provided with anode filling opening, the cathode
Room is additionally provided with cathode filling opening；The aerator includes interconnected aerator and aeration head, further includes flow controller；
The external circuit is additionally provided with contactor.
9. device according to claim 7, it is characterised in that：The material of the anode electrode is graphite felt, carbon paper, carbon
Cloth, graphite rod or stainless (steel) wire；The material of the cathode electrode is graphite felt, carbon paper, carbon cloth, graphite rod or stainless (steel) wire.
10. device according to claim 9, it is characterised in that：The graphite felt is to pass through pretreated graphite felt, described
Preprocess method is that will be placed in the water-soluble of hydrogen peroxide that mass fraction is 9~11% without the graphite felt of modified metal oxide
In liquid, 1~3h is handled at 85~95 DEG C, then handles 1~3h at the same temperature with water, dry.
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