CN103739161A - Low-energy-consumption degradation-resistant organic wastewater recycling method - Google Patents

Low-energy-consumption degradation-resistant organic wastewater recycling method Download PDF

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CN103739161A
CN103739161A CN201310732732.5A CN201310732732A CN103739161A CN 103739161 A CN103739161 A CN 103739161A CN 201310732732 A CN201310732732 A CN 201310732732A CN 103739161 A CN103739161 A CN 103739161A
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organic wastewater
mfc
mbr
degradation
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李秀芬
游晓伟
王新华
任月萍
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Jiangnan University
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Jiangnan University
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Abstract

The invention provides a low-energy-consumption degradation-resistant organic wastewater recycling method, belonging to the technical field of degradation-resistant wastewater resourcezation. After degradation-resistant organic wastewater is treated by pH adjustment, hydrolytic acidification, Fenton oxidization and electrolytic pretreatment, the degradation-resistant organic wastewater is treated by adopting a membrane bioreactor (an aerobiotic biotechnology) coupled with a microbial fuel battery (an anaerobic biotechnology), electric energy consumption of the membrane bioreactor is compensated by electric energy generated by the microbial fuel battery, and meanwhile, the surface of a membrane bioreactor assembly as the negative pole of the microbial fuel battery is charged by negative electricity to generate electrostatic repulsion among membrane surface contaminants so as to effectively alleviate membrane pollution. Compared with conventional treatment processes, wastewater treatment energy consumption per ton is reduced by 40-70%, the COD (Chemical Oxygen Demand) and the ammonium-nitrogen removal rate of the system reach 92.0-99.5%, and the effluent quality accords with a first level standard A in Pollutant Discharge Standard of Municipal Wastewater Treatment Plant of China (GB18918-2002) and the reuse demand in the industry. The method provided by the invention is scientific and reasonable in technology, and has important meaning for recycle of degradation-resistant organic wastewater.

Description

A kind of method of less energy-consumption Reuse of non-biodegradable organic wastewater
Technical field
A method for less energy-consumption Reuse of non-biodegradable organic wastewater, belongs to organic wastewater with difficult degradation thereby resource technology field.
Background technology
In recent years, as the advantage combination of waste water physics and biologic treating technique, so that excess sludge production is low, is good at, with organic wastewater resources regeneration (or reuse) and harmless membrane bioreactor (Membrane Bioreactor, the MBR) technology that turns to ultimate aim, in treatment of Organic Wastewater field, is widely used with efficient denitrification.According to statistics, China puts into operation or has exceeded 300 in the MBR treatment of Organic Wastewater engineering of building, wherein, and nearly 10 covers of ton MBR system.But practice at home and abroad shows, it is the major obstacle of restriction MBR steady running all the time that running cost and film pollute.Microbiological fuel cell (Microbial Fuel Cell, MFC) be one by difficult degradation thing in anode electrogenesis microbial film degradation of organic waste water and produce the new technology of sustainable electric energy.As all fuel cells, MFC generating is not that fuel (the difficult degradation thing in waste water or waste) is burnt, but under anaerobic from fuel molecule, strip electronics (being the electronics that Microorganism respiration produces dirt), and be delivered to oxygen by predetermined approach (electrode and external circuit), by the Conversion of energy that is originally used for oxidative phosphorylation biosynthesizing ATP, be electricity, wherein microorganism is the catalyzer of biochemical reaction.The electricity generation process of MFC realizes by the oxidation of anode difficult degradation thing (electron donor) and the reduction of negative electrode oxygen (electron acceptor(EA)).But, as one of Anaerobic Microbiological Treatment Technology, MFC is difficult to obtain good effluent quality, be combined with techniques such as nitrifying process, sequencing batch reactor, blodisc, bio-contact oxidations, even MFC is placed in to the aeration tank of activated sludge process, can improve MFC effluent quality, but said process all cannot effectively be removed the suspended substance in system water outlet, is difficult to reuse.
The water quality of difficult for biological degradation organic waste water has following features: (1) water quality complexity, and by product is many, and reaction raw materials is often the compound of solvent based material or ring texture, has increased the intractability of waste water; (2) in waste water due to raw material reaction not exclusively and raw material or produce in a large amount of solvent mediums of use entered waste water system, cause COD and BOD 5concentration is high; (3) hazardous and noxious substances is many, many difficult degradation pollutents are poisonous and hazardous to microorganism, as halogen compounds, nitro-compound, the dispersion agent with germicidal action or tensio-active agent etc., wherein most being put in the Black List of China and U.S. EPA Environment Priority control pollutent: (4) chroma in waste water is high; (5) saltiness is high.Common salt is mainly muriate, vitriol and phosphoric acid salt etc.: the nutritive element serious disproportion that (6) microorganism needs, and except nitrogenous height, difficult degradation thing mostly wherein is difficult for biological degradation, toxic compound, and phosphoric comparatively lacks; (7) change of water quality is large, and biodegradability is poor, and the difficult degradation thing that relative molecular weight is large is preponderated, and BOD/COD value is very low, is near or below 0.1.
Make a general survey of Processing Technology Research and the engineering practice for organic wastewater with difficult degradation thereby both at home and abroad, can find mainly to have following problem: the efficiency that (1) ordinary method is processed waste water is not high, some toxic compound is difficult to remove, and water outlet can not really reach emission standard; (2) some special process or facility investment are larger, and the cost of processing waste water is higher, is difficult to apply; (3) system is comparatively complicated, and operation is had relatively high expectations, and stability is to be improved.
The present invention is take organic wastewater with difficult degradation thereby as handling object, the MBR (aerobe technology) that has proposed coupling MFC (anaerobe technology) processes organic wastewater with difficult degradation thereby new technology, this technology has following advantage: 1. pretreatment unit can be converted into the hardly degraded organic substance in organic waste water the small organic molecule of readily biodegradable, improves the treatment effect of subsequent biological treatment unit.2. in organic waste water, most of hardly degraded organic substance is in MFC anode generation oxidizing reaction (reaction formula 1), and the electronics of generation is delivered to MFC negative electrode via anode and external circuit, and the electric energy of recovery can be used for compensating the high running cost of MBR.3. the proton that MFC anodic oxidation produces passes through anoxic unit with current and arrives MBR aerobic unit (being MFC cathode compartment), generate water (reaction formula 2) with electronics and combination with oxygen, eliminated the easy acidifying of common MFC anode, feedback inhibition electrogenesis microorganism active problem.4. the residue difficult degradation thing after MFC anodic oxidation also passes through anoxic unit with current and arrives MBR aerobic unit, and further aerobic mineralising is removed (reaction formula 3), and MBR film filtration effluent water quality is good.5. be there is nitration denitrification reaction in anoxic unit, and membrane module can efficiently be tackled nitration denitrification bacterium, system denitrification effect good (reaction formula 4-7) simultaneously.6. the membrane module in MBR, simultaneously as MFC negative electrode (also claiming conduction microfiltration membrane), can be between MBR film surface and film surface pollution thing electrostatic repulsion is provided, and effectively alleviates film and pollutes.
C 6H 12O 6+6H 2O→6CO 2+24H ++24e -??(1)
4H ++O 2+4e -→2H 2O??(2)
C 6H 12O 6+6O 2→6CO 2+6H 2O??(3)
NH 4 ++1.5O 2→NO 2 -+2H ++H 2O??(4)
NO 2 -+1.5O 2→NO 3 -??(5)
NO 2 -+3H +→0.5N 2+H 2O+OH -??(6)
NO 3 -+5H +→0.5N 2+H 2O+OH -??(7)
Summary of the invention
The object of the invention is to invent the method for the Reuse of non-biodegradable organic wastewater that a kind of energy consumption is low, effluent quality is good.
Technical matters of the present invention comprises following step:
1, water inlet: organic wastewater with difficult degradation thereby, COD concentration is 1000~10000mg/L, and ammonia nitrogen concentration is 100~2000mg/L, and pH value is that 1~14, B/C ratio is less than 0.2;
2, pretreatment unit: first organic wastewater with difficult degradation thereby is squeezed into pre-unit by intake pump and carried out pre-treatment, hydraulic detention time (Hydraulic Residence Time, HRT) is 12~48h, temperature is 15~35 ℃; Pretreatment process comprises pH regulator, acidication, Fenton oxidation, electrolysis.
3, anaerobic treatment unit: pretreatment unit water outlet is carried out anaerobic treatment from the anolyte compartment that flow to MFC, and HRT is 12~48h, and temperature is 15~35 ℃, and anode material is carbon felt, carbon cloth, graphite and modifying and decorating material thereof;
4, anoxic unit: anaerobic unit water outlet is from flowing to anoxic unit, and HRT is 12~48h, and temperature is 15~35 ℃, and dissolved oxygen concentration is 0.1~1.0mg/L;
5, aerobic unit: anoxic unit water outlet is from flowing to MBR aerobic unit, it is MFC cathode compartment, HRT is 12~24h, temperature is 15~35 ℃, dissolved oxygen concentration is 2.0~6.0mg/L, the MBR membrane module MFC negative electrode of holding concurrently, material is stainless (steel) wire, non-woven fabrics, carbon felt, carbon cloth conducting polymer modified or preparation
6, exhaust unit: discharge reuse through MBR water outlet, wet-pit and pipeline through aerobic unit waste water after treatment.
Advantage of the present invention
1, pretreatment unit can make the most of toxic compounds in waste water be converted into small organic molecule, reduces COD, thereby improves the biodegradability of waste water, meanwhile, pH value is adjusted to neutrality;
2, in organic waste water there is anaerobic oxidation reaction in most of difficult degradation thing in MFC anolyte compartment, and the electronics of generation is delivered to MFC negative electrode via MFC anode and external circuit, by extrernal resistance, reclaims its electric energy and for compensating MBR running cost;
3, the proton that MFC anodic oxidation produces passes through anoxic unit with current and arrives MBR aerobic unit (being MFC cathode compartment), generates water with electronics and combination with oxygen, has eliminated the problem of the easy acidifying of common MFC anode, feedback inhibition electrogenesis microorganism active;
4, the residue difficult degradation thing after MFC anodic oxidation also passes through anoxic unit with current and arrives MBR aerobic unit, and further aerobic mineralising is removed;
5, be there is nitration denitrification reaction in the existence of anoxic unit, and membrane module can efficiently be tackled nitration denitrification bacterium simultaneously, and system denitrification effect is good;
6, the membrane module in MBR, simultaneously as MFC negative electrode (also claiming conduction microfiltration membrane), can be between MBR film surface and film surface pollution thing electrostatic repulsion is provided, and effectively alleviates film and pollutes;
7, compared with conventional processes, ton treatment of Organic Wastewater Energy Intensity Reduction 40%~70%, system COD and ammonia nitrogen removal frank are 92.0%~99.5%, and effluent quality meets one-level A standard and the interior reuse requirement of industry in China's urban wastewater treatment firm pollutant emission standard (GB18918-2002).
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1:MFC anode adopts carbon felt, and MBR membrane module adopts Graphene+polyvinylidene difluoride (PVDF) to modify non-woven fabrics.System influent quality is as follows: COD concentration is 1000mg/L, ammonia nitrogen 100mg/L, and pH value is that 8, B/C ratio is 0.2; Pre-treatment adopts hydrolysis acidification method, and HRT is 12h; The HRT of anaerobic unit is 8h; Anoxic unit HRT is 10h, and dissolved oxygen concentration is 0.2mg/L; The HRT of aerobic unit is 6h, and dissolved oxygen concentration is 4.0mg/L; Temperature is 25 ℃.
Embodiment 2:MFC anode adopts carbon cloth, and MBR membrane module adopts Polyaniline-modified stainless (steel) wire.System influent quality is as follows: COD concentration is 5000mg/L, ammonia nitrogen 1000mg/L, and pH value is that 3, B/C ratio is 0.1; Pre-treatment adopts Fenton oxidation method, and HRT is 0.5h, regulates pH value to 7.0; The HRT of anaerobic unit is 24h; Anoxic unit HRT is 12h, and dissolved oxygen concentration is 0.5mg/L; The HRT of aerobic unit is 8h, and dissolved oxygen concentration is 2.0mg/L; Temperature is 30 ℃.
Embodiment 3:MFC anode adopts graphite, and MBR membrane module adopts graphene modified carbon cloth.System influent quality is as follows: COD concentration is 10000mg/L, ammonia nitrogen 2000mg/L, and pH value is that 12, B/C ratio is 0.1; Pre-treatment adopts electrolytic process, and HRT is 0.5h, regulates pH value to 7.0; The HRT of anaerobic unit is 30h; Anoxic unit HRT is 20h, and dissolved oxygen concentration is 0.1mg/L; The HRT of aerobic unit is 12h, and dissolved oxygen concentration is 6.0mg/L; Temperature is 35 ℃.

Claims (5)

1. a method for less energy-consumption Reuse of non-biodegradable organic wastewater, is characterized in that:
(1) water inlet: organic wastewater with difficult degradation thereby, COD concentration is 1000~10000mg/L, and ammonia nitrogen concentration is 100~2000mg/L, and pH value is that 1~14, B/C ratio is less than 0.2;
(2) pretreatment unit: first organic wastewater with difficult degradation thereby is squeezed into pre-unit by intake pump and carried out pre-treatment, hydraulic detention time (Hydraulic Residence Time, HRT) be 12~48h, temperature is 15~35 ℃, and pretreatment process comprises pH regulator, acidication, Fenton oxidation, electrolysis.
(3) anaerobic treatment unit: pretreatment unit water outlet is from flowing to microbiological fuel cell (Microbial Fuel Cell, MFC) anolyte compartment carries out anaerobic treatment, HRT is 12~48h, temperature is 15~35 ℃, and anode material is carbon felt, carbon cloth, graphite and modifying and decorating material thereof;
(4) anoxic unit: anaerobic unit water outlet is from flowing to anoxic unit, and HRT is 12~48h, and temperature is 15~35 ℃, and dissolved oxygen concentration is 0.1~1.0mg/L;
(5) aerobic unit: anoxic unit water outlet is from flowing to membrane bioreactor (Membrane Bioreactor, MBR) aerobic unit, it is MFC cathode compartment, HRT is 12~24h, temperature is 15~35 ℃, dissolved oxygen concentration is 2.0~6.0mg/L, the MBR membrane module MFC negative electrode of holding concurrently, and material is conducting polymer modified stainless (steel) wire, non-woven fabrics, carbon felt, carbon cloth;
(6) drainage cell: discharge reuse through MBR water outlet, wet-pit and pipeline through aerobic unit waste water after treatment.
2. the method for a kind of less energy-consumption Reuse of non-biodegradable organic wastewater according to claim 1, it is characterized in that: the proton that the organism in waste water produces in MFC anodic oxidation passes through anoxic unit with current and arrives MBR aerobic unit (being MFC cathode compartment), generate water with electronics and combination with oxygen, eliminated the problem of the easy acidifying of common MFC anode, feedback inhibition electrogenesis microorganism active.
3. the method for a kind of less energy-consumption Reuse of non-biodegradable organic wastewater according to claim 1, is characterized in that: the residual organic substances after MFC anodic oxidation is also passed through anoxic unit with current and arrived MBR aerobic unit, and further aerobic mineralising is removed.
4. the method for a kind of less energy-consumption Reuse of non-biodegradable organic wastewater according to claim 1, is characterized in that: nitrification and denitrification reaction is occurred anoxic unit, and MBR membrane module can efficiently be tackled nitration denitrification bacterium simultaneously, and system denitrification effect is good.
5. the method for a kind of less energy-consumption Reuse of non-biodegradable organic wastewater according to claim 1, it is characterized in that: the membrane module in MBR aerobic unit is simultaneously as MFC negative electrode (also claiming conduction microfiltration membrane), can be between MBR film surface and film surface pollution thing electrostatic repulsion is provided, effectively alleviate film and pollute.
CN201310732732.5A 2013-12-26 2013-12-26 Low-energy-consumption degradation-resistant organic wastewater recycling method Pending CN103739161A (en)

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CN106746230A (en) * 2016-12-29 2017-05-31 东南大学 Based on electric fenton sewage processing system and processing method that row array type wetland microbiological fuel cell is powered
CN106986499A (en) * 2017-05-04 2017-07-28 张颖柏 A kind of processing method of printing ink wastewater
CN107919484A (en) * 2017-11-09 2018-04-17 太原理工大学 Direct borohydride fuel cell that is a kind of while handling organic wastewater

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CN106746230A (en) * 2016-12-29 2017-05-31 东南大学 Based on electric fenton sewage processing system and processing method that row array type wetland microbiological fuel cell is powered
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CN106986499A (en) * 2017-05-04 2017-07-28 张颖柏 A kind of processing method of printing ink wastewater
CN107919484A (en) * 2017-11-09 2018-04-17 太原理工大学 Direct borohydride fuel cell that is a kind of while handling organic wastewater

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