CN104496109B - The device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby - Google Patents
The device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
Abstract
The present invention relates to the device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, first organic waste water is carried out electrolysis by compound electric solution, the macromole organic pollutant electrolysis allowing to degrade generates the low molecule organic pollutant that can volatilize, and obtains the waste water to be extracted comprising organic composition and inorganic components; Then utilize and to organic composition, there is high permeability and inorganic components is had to the membrane extraction system of crown_interception, organic composition is separated with inorganic components; Last organic composition enters biological treatment system and carries out biological degradation, completes the process of high salt organic wastewater with difficult degradation thereby.The present invention is by the coupling of combined electrolysis and perstraction technique, combined electrolysis intermediate product is worked in coordination with mutually with membrane extraction system works mechanism, guarantee generate material rapidly and efficiently by membrane extraction system, realize effectively being separated of organic composition and inorganic components, again through biological treatment, good degrading effect, and reduce saltiness.
Description
Technical field
The invention belongs to field of environment protection, particularly relate to the device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby.
Background technology
A large amount of Persistent organic pollutants during organic waste water contains, this kind of material has good chemical stability in water, containing multiple, there is bio-toxicity or " three causing property " organism, generally be difficult to direct biological degradation, row biological degradation again after many employing chemical oxidation pre-treatment adjustment biochemistry at present, the degraded product of its chemical oxidation mostly is aromatic compounds, and its biological degradation is also by restriction to a certain extent.Simultaneously, engineering practice proves, can produce microorganism growth and degraded activity when salt quality total in waste water reaches more than 1% and suppress even toxic action, organic degraded is made to be difficult to go on, biological process is made to be difficult to use in the process of brine waste, so be high content of salt when the massfraction of total salt is more than 1% in waste water.Secondly, high salinity waste water produces larger negative interaction to pipe network and equipment, can directly cause river water quality salinity to significantly improve after entering environment, accelerates salting of soil, brings serious negative impact to the ecosystem.Therefore, saltiness becomes one of important indicator of industrial wastewater discharge standard gradually.Comprehensive above two aspects, exploring high salinity refractory organic waste water process new technology has become one of focus of field of Environment Protection concern.
Summary of the invention
The object of the invention is to solve above-mentioned problems of the prior art, a kind of effective degrade organic compounds is provided, reduce the device and method of the electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby of saltiness.
The technical scheme of degradation method of the present invention is:
1) organic waste water is carried out electrolysis by compound electric solution, obtain the waste water to be extracted comprising organic composition and inorganic components; Described organic waste water contains inorganic salt, mineral acid and macromole organic pollutant, and the massfraction of described inorganic salt is more than 1%; DSA electrode pair and DSA-carbon dioxide process carbon electrode is adopted to carry out electrolysis to the multiple combined type electrolysis reactor formed in described compound electric solution;
2) by step 1) waste water to be extracted that obtains to introduce in membrane extraction system and to be separated with inorganic components by organic composition;
3) step 2 is made) isolated organic composition enters biological treatment system and carries out biological degradation, until the water outlet of biological treatment system reaches emission standard, thus completes the process of high salt organic wastewater with difficult degradation thereby.
Described step 1) in macromole organic pollutant in organic waste water comprise aromatic organic compounds.
Described step 1) in the electrolytic condition that adopts of compound electric solution be: current density: 80 ~ 180A/m
2, voltage: 10 ~ 15v, electrolysis time: 10 ~ 20min.
Described step 2) in membrane extraction system comprise the tube side that is made up of tubular silicon rubber diaphragm and the outer sheathed shell side of tube side; Waste water to be extracted is introduced into tube side internal cavities, organic composition wherein enters shell side through silicone rubber membrane membranous wall, enter biological treatment system through shell-side outlet again and carry out biological degradation, inorganic components is recycled from tube side internal cavities through tube side outlet discharge.
Described step 3) in the water outlet of biological treatment system enter shell side again through shell side inlet and use as the strip liquor of membrane extraction system, or rear discharge up to standard.
Described biological treatment system comprises the biophase of taming in advance through organic waste water, and described biophasic sludge concentration is 5000 ~ 8000mg/L, and Dissolved Oxygen concentration Control is at 1.5 ~ 2.0mg/L.
The technical scheme of apparatus of the present invention is:
Comprise electrolyzer, membrane extraction system and biological treatment system, described electrolyzer comprises multiple combined type electrolysis reactor, multiple combined type electrolysis reactor by DSA electrode pair and DSA-carbon dioxide process carbon electrode to forming; Membrane extraction system comprises tube side and the outer sheathed shell side of tube side, and described tube side is the silicone rubber membrane of some tubular types, and the water side of electrolyzer is connected with silicone rubber membrane inlet end, and the exit end of silicone rubber membrane connects recycling system; The exit end of shell side connects the inlet end of biological treatment system, and the exit end of biological treatment system and the inlet end of shell side are connected to form loop, and the exit end of biological treatment system also connects blowdown system.
Described DSA electrode is covered with paint, lacquer, colour wash, etc. rare elements or its oxide compound or titanyl compound and is prepared from titanium base, and described rare elements comprises tin, antimony or ruthenium.
Adopt some to take polysulfone hollow fibre as polydimethylsiloxane tubular membrane or the Polymethyl methacrylate tubular membrane of carrier in described membrane extraction system, in plexi-glass tubular, form tube side and shell side by epoxy sealing.
Described silicone rubber membrane comprises 350 ~ 500, and film bore is 1mm, thickness 0.1mm, and length is 1m.
Compared with prior art, the present invention has following useful technique effect:
The present invention adopts the technology of combined electrolysis-extractive membrane biological reactors coupling, and combining with Graphite Electrodes by adopting metal anode DSA and producing OH free radical is core oxidation mechanism, in the mineral acid in organic waste water, the inorganic salt content in reduction water; By DSA electrode pair, DSA-carbon dioxide process carbon electrode to the combined electrolytic reactor that comes from different backgrounds and possess different abilities, for the organic waste water of the high-concentration hardly-degradable organic pollutant containing 2000mg/L, can be volatile low molecule organic pollutant by wherein more than 90% macromole organic pollutant degradation, if containing Cl in the organic waste water processed in the present invention simultaneously
-will as analysing chloride electrode on, the then anode in electrode pair, by Cl
-be direct oxidation into chlorine and reduce Cl
-content, effectively cuts down the inorganic salt content in water, is beneficial to brine waste qualified discharge; Then this low molecule organic matter is separated with acid ion with inorganic ion with the organism that cannot thoroughly decompose by membrane extraction system, percentage extraction is more than 90%, organic content in brine waste is reduced to below 100mg/L, is beneficial to the industrial cycle reuse of salt solution and sour water; And the low molecule organic pollutant that organic composition and hardly degraded organic substance and electrolysis generate finally enters biological treatment system and degrades thoroughly, complete the efficient removal of high salinity Persistent organic pollutants, in the present invention, organic pollutant removal rate can reach 85 ~ 92%, can realize the qualified discharge of high salinity refractory organic waste water.Because the present invention can adopt dissimilar combined electrolysis technique, make this technology be applicable to all kinds of high concentrated organic wastewater, finally reach promotion cleaner production, enhance productivity, reduce the object of processing cost simultaneously.The present invention is directed to high salinity refractory organic waste water feature, combined electrolysis-spe membrane biological coupling art breading high salinity difficult degradation organic chemical waste water is proposed, combined electrolysis intermediate product is worked in coordination with mutually with membrane extraction system works mechanism, guarantee generate material can rapidly and efficiently by membrane extraction system, realize inorganic salt, mineral acid is effectively separated with combined electrolysis degraded product, again through biological treatment, good degrading effect; The technology of the present invention content is high, strong innovation, has a extensive future, and for the cleaner production of promotion traditional chemical industry synthesis industry, promotes that the development of related industries is of great immediate significance.
Further, the present invention, by regulating the electrolytic condition in compound electric solution, can control the high salinity of different sources, the electrolytic process of peracidity organic waste organic pollutants and product types.
Apparatus of the present invention are by arranging the electrolyzer containing multiple combined type electrolysis reactor, organic waste water is degraded, then utilize silicone rubber membrane as the extraction phase of membrane extraction system, to organic composition, there is high permeability and to inorganic components, there is crown_interception, the organic composition comprising intermediates is effectively separated with inorganic components, make brine waste enter recycling system and reach cyclically utilizing, as the salting-out process for Dyestuff synthesis; And make organic composition enter the outer further biological degradation of biological treatment system of film, the shell side inlet of biological treatment system and membrane extraction system is connected to form loop again, the waste water after biological treatment system process is enable again to enter membrane extraction system, as strip liquor recycle, or rear discharge up to standard; Thus realizing the efficient removal of high salinity Persistent organic pollutants, structure is simple, and easy to operate, degradation rate is high, and can adopt dissimilar electrolysis reactor in the present invention, makes the present invention be applicable to the degraded of all kinds of high concentrated organic wastewater.
Further, in the present invention membrane extraction system adopt with polysulfone hollow fibre be the polydimethylsiloxane tubular membrane of carrier or Polymethyl methacrylate tubular membrane as spe membrane, effectively ensure effect of extracting.
Further, can selective membrane pipe quantity according to water outlet small molecular organic contamination substrate concentration after electrolysis in the present invention, and then determine the surface-area of total spe membrane, water outlet after electrolysis, through this membranous system, effectively improves effect of extracting and extraction efficiency.
Accompanying drawing explanation
Fig. 1 is Technology schema of the present invention;
Fig. 2 is structured flowchart of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further details:
With reference to Fig. 1, the present invention is directed to high salt organic waste water and be difficult to a biodegradable difficult problem, invent a kind of electrolysis-extraction-biological composite handling arrangement and method.
The present invention includes electrolyzer, membrane extraction system and biological treatment system.The water side of electrolyzer is connected with the tube-side inlet end of membrane extraction system, tube side exit end connects the recycling system for reclaiming inorganic ion and acid ion (inorganic components), the shell-side outlet end of membrane extraction system connects the biological treatment system inlet end for the treatment of extracting the organic composition obtained, the exit end of biological treatment system and the inlet end of shell side are connected to form loop, and the exit end of biological treatment system also connects blowdown system.
Wherein, electrolyzer contains by 2 ~ 4 DSA electrode pairs and 2 ~ 4 DSA-carbon dioxide process carbon electrodes the multiple combined type electrolysis reactor formed with combined in any order, wherein DSA matrix adopts titanium metal, according to different needs, surface of metal titanium is covered with paint, lacquer, colour wash, etc. tin, antimony or ruthenium respectively or is covered with paint, lacquer, colour wash, etc. the oxide coating of titanium, tin, antimony or ruthenium, when organism is difficult to electrolysis time, need noble potential, needing the electrode surface of noble potential to add a small amount of platinum, form metal anode (DSA).In the present invention, electrolytic condition adopts: current density: 80 ~ 180A/m
2, voltage: 10 ~ 15v, electrolysis time: 10 ~ 20min; The flow control that membrane extraction system is introduced in electrolysis water outlet is 50 ~ 80L/h.
Membrane extraction system comprises the tube side of shell side and shell side inside, for different electrolysates, need the spe membrane material selecting preparation adaptive, ensure the high permeability of small molecules organic pollutant and have retaining of inhibiting material to inorganic salt, acid ion etc. to biological treatment system.The selection of spe membrane material, mainly determine according to the octanol water partition coefficient of film component and organic octanol water partition coefficient to be extracted, more close, organic effect of extracting is better, is ensured by the nonporosity of film to retaining of inorganics; So select tubular silicon rubber diaphragm as the tube side of spe membrane, utilize the composite of polydimethylsiloxane, Polymethyl methacrylate material and different sizing agent, membrane-forming agent preferably prepare membrane extraction system; In the present invention, employing 350 ~ 500 take polysulfone hollow fibre as polydimethylsiloxane tubular membrane or the Polymethyl methacrylate tubular membrane of carrier, every root film bore is 1mm, thickness 0.1mm, length is 1m, in plexi-glass tubular, tube side and shell side is formed by epoxy sealing, wherein, tube side comprises film pipe internal passages and membranous wall, membranous wall forms the film phase that can be separated organic composition and inorganic components, organic composition can be dissolved in film mutually in and spread, inorganic components is insoluble to film phase.
Biological treatment system comprises activated sludge tank, and wherein containing the biophase of taming in advance through organic waste water, biophasic sludge concentration is 5000 ~ 8000mg/L, and Dissolved Oxygen concentration Control is at 1.5 ~ 2.0mg/L.
Key step and the principle of degradation method of the present invention are as follows:
First will containing inorganic salt, mineral acid and the pre-treatment of aromatic series macromole organic pollutant high salinity refractory organic industrial sewage, mainly remove the large granular impurity in waste water, wherein inorganic salt massfraction is more than 1%, can be any inorganic salt; The massfraction of mineral acid, 2 ~ 5%, comprises sulfuric acid etc.; By one or more mixtures that the macromole organic pollutant degradation of high-concentration hardly-degradable is in the volatile low molecule organic pollutants such as phenols, aldehydes or carboxylic-acid by compound electric solution, obtain the waste water to be extracted comprising organic composition and inorganic components, wherein organic composition is low molecule organic pollutant and the macromole organic pollutant that cannot thoroughly degrade, and inorganic components is inorganic ion and acid ion; Utilize in the present invention the adjustment of electrolytic condition to control the high salinity of different sources, the electrolytic process of peracidity organic waste organic pollutants and product types;
Then electrolysis water outlet and waste water to be extracted are that 50 ~ 80L/h enters in the tube side of membrane extraction system with flow, hydrophobic silicone rubber membrane is utilized to be separated with inorganic components by this organic composition as extraction phase, sepn process is: because inorganic components cannot be dissolved in and pass silicone rubber membrane, so directly from the inner holding tank entering recycling system through tube side outlet of tube side, brine waste is made to reach cyclically utilizing or advanced treatment, such as the salting-out step etc. of Dyestuff synthesis process; Organic composition, according to its dissolving on silicone rubber membrane and the difference of velocity of diffusion, enters film phase (i.e. the membranous wall of spe membrane) from the blended liquid phase of waste water to be extracted step by step; Enter shell side from the back extraction of film phase under the promotion of final concentration difference inside and outside film, namely enter shell side through tube wall, and enter biological treatment system through shell-side outlet;
Last organic composition is further biological degradation under biophasic effect, thus realizes the efficient removal of high salinity Persistent organic pollutants; The water outlet of biological treatment system reaches emission standard, as " textile dyeing and finishing industrial water pollution thing emission standard " (GB4287-2012), so can directly discharge, also can enter shell side through shell side inlet to use as the strip liquor of membrane extraction system, can effectively ensure back extraction continue carry out, save energy and cost.
Due to dissimilar combined electrolysis technique can be adopted, the present invention is made to be applicable to the degraded of all kinds of high concentrated organic wastewater.Finally reach promotion cleaner production, enhance productivity, reduce the object of processing cost simultaneously.
The technology of the present invention core is the technical finesse high salinity refractory organic industrial sewage adopting combined electrolysis-extractive membrane biological reactors coupling, according to the feature of high salinity difficult degradation organic chemical waste water, adopting metal anode (DSA) to combine with Graphite Electrodes and producing OH free radical is core oxidation mechanism, the method coordinating titanium base to cover with paint, lacquer, colour wash, etc. the different rare elements such as precious metal or its oxide compound prepares metal anode (DSA), by DSA electrode pair, DSA-carbon dioxide process carbon electrode is to the combined electrolytic reactor degradation of organic substances that comes from different backgrounds and possess different abilities, if the inorganic ion contained in organic waste water comprises Cl
-, then the anode in electrode pair will as analysing chloride electrode, by Cl
-be oxidized to chlorine and reduce Cl
-content, salts contg in effective reduction water, catalyzed oxidation decomposition is carried out to macromolecular hardly degraded organic substance simultaneously, the organism that cannot thoroughly decompose then enters the outer biological treatment system of film through spe membrane, and enter the hardly degraded organic substance of biological treatment system and intermediates is degraded thoroughly under the effect of specificity microorganism, finally realize the qualified discharge of high salinity refractory organic waste water.
Metal anode of the present invention is by the multiple combined type electrolysis reactor degradation of organic substances by formation right to DSA electrode pair, DSA-carbon dioxide process carbon electrode.Electrolytic condition used is: current density: 80 ~ 180 (A/m
2), voltage: 10 ~ 15v, electrolysis time: 10 ~ 20min.In electrolytic process, by the combination of electrode, allow waste water first through analysing chloride electrode, and then through analysing oxygen electrode, allowing as far as possible and analysing chlorine and analyse oxygen process separately, the work-ing life of electrode and the efficiency of COD removal can be improved.Volatile organic compound and the lower boiling systems such as phenols, aldehydes or carboxylic-acid is converted into by this step hardly degraded organic substance more than 90%, metal anode (DSA) combines with Graphite Electrodes and produces OH free radical simultaneously, makes acid waste water under the condition not adding alkali, realize the effect of chemical neutralization.External phase (referring to the electrolysis water outlet continuing to enter extracting system) density is 0.95 ~ 1kg/m
3according to water outlet small molecular organic contamination substrate concentration selective membrane pipe quantity after electrolysis, determine surface-area, this membranous system is being passed through in water outlet after electrolysis, inorganic ion and acid ion are still retained in tubular film inside, enter cycling and reutilization system by film internal passages.Discharge after small molecules organic pollutant after electrolysis and the macromole organic pollutant that cannot thoroughly degrade enter the process of biological treatment system (percentage extraction reaches more than 90%) standard biologic method through spe membrane.Difficult point of the present invention is the coupling of combined electrolysis and perstraction technique, combined electrolysis intermediate product is worked in coordination with mutually with spe membrane working mechanism, guarantee generate material can rapidly and efficiently by spe membrane, realize inorganic salt, strong acid be effectively separated with combined electrolysis degraded product.And make saliferous (acid) Organic substance in water content be reduced to below 100mg/L, realize the industrial cycle reuse of salt solution and sour water.
Embodiment one
Certain organic dye synthesis scale wastewater treatment:
Main containing azoic dyestuff directly dark brown and acid scarlet in this enterprise wastewater.Concentration is all at about 2000mg/L, and the salinity in raw wastewater is up to 5%, and the massfraction of mineral acid is 2 ~ 5%.Conventional Biochemical method is difficult to be effective.In the present invention, first this organic waste water is introduced and be equipped with in the electrolyzer of titanium base DSA electrode pair, control current density: 120 (A/m
2), voltage: 12v, electrolysis time: 15min.In electrolytic process, changing cathode and anode directions by changing set banister direction, thus analysing oxygen in altering reactor, analyse the carrying out of the electrolytic reactions such as chlorine.Along with the waste water that carries out of electrolysis fades gradually, show that macromole organic pollutant structure changes, chromophoric group or auxochrome group are damaged, and are degraded to one or more mixtures in the volatile low molecule organic pollutants such as phenols, aldehydes or carboxylic-acid.Spe membrane treatment system is introduced in electrolysis water outlet, and flow control is 50L/h, and temperature is room temperature.The mould material used is take polysulfone hollow fibre as the polydimethylsiloxane tubular membrane of carrier.Membrane module is containing composite tube type spe membrane 350, and film bore is 1mm, thickness 0.1mm, and length is 1m.Above-mentioned composite tube type film epoxy sealing, in plexi-glass tubular, forms shell side and tube side.Respectively electrolysis water outlet is connected with shell side with the tube side of membrane module with activated sludge tank with pump, forms each self circular loop.Electrolysis wastewater enters tubular membrane inside, and in bio-reactor, supernatant liquor circulation enters shell side as back extraction phase.Small organic molecule then in waste water to be extracted and the larger molecular organics being difficult to degrade enter back extraction phase, by being pumped into bio-reactor through after film phase (spe membrane membranous wall); The holding tank then entering recycling system from the internal passages of spe membrane pipe containing the waste water of acid ion, inorganic ion treats reuse.Bio-reactor volume is 500L, and sludge concentration is 6000mg/L, and regularly supplement the nutrients material, and be activated sludge aeration with pneumatic pump, Dissolved Oxygen concentration Control is at about 2.0mg/L.Combined electrolysis-extraction-biological treatment reactor of the present invention runs 1000h continuously, and in raw wastewater, two class azoic dyestuff clearances can reach 85 ~ 92%.
Embodiment two
Main containing anthraquinone dyes acid blue and aniline in certain organic waste water, concentration is at about 2300mg/L, and the salinity in waste water is up to 10%, and the massfraction of sulfuric acid is 2%.Conventional Biochemical method is difficult to be effective.In the present invention, first this organic waste water is introduced and be equipped with DSA electrode pair and DSA-carbon dioxide process carbon electrode in the electrolyzer of the multiple combined type electrolysis reactor formed, control current density: 180 (A/m
2), voltage: 15v, electrolysis time: 20min.In electrolytic process, changing cathode and anode directions by changing set banister direction, thus analysing oxygen in altering reactor, analyse the carrying out of the electrolytic reactions such as chlorine.Along with the waste water that carries out of electrolysis fades gradually.Show that its structure changes, chromophoric group or auxochrome group are damaged.Spe membrane treatment system is introduced in electrolysis water outlet, and flow control is 80L/h, and temperature is room temperature.The mould material used is take polysulfone hollow fibre as the Polymethyl methacrylate tubular membrane of carrier, and membrane module is containing composite tube type spe membrane 500, and film bore is 1mm, thickness 0.1mm, and length is 1m.Above-mentioned composite tube type film epoxy sealing, in plexi-glass tubular, forms shell side and tube side.Respectively electrolysis water outlet is connected with shell side with the tube side of membrane module with activated sludge tank with pump, forms each self circular loop.Electrolysis wastewater enters tubular membrane inside, and in bio-reactor, supernatant liquor circulation enters shell side as back extraction phase.Small organic molecule then in waste water to be extracted and the larger molecular organics being difficult to degrade enter back extraction phase through film, mutually afterwards by being pumped into bio-reactor; The holding tank then entering recycling system from the internal passages of spe membrane pipe containing the waste water of acid ion, inorganic ion treats reuse.Bio-reactor volume is 500L, and sludge concentration is 8000mg/L, and regularly supplement the nutrients material, and be activated sludge aeration with pneumatic pump, Dissolved Oxygen concentration Control is at about 1.8mg/L.Combined electrolysis-extraction-biological treatment reactor of the present invention runs 1000h continuously, and in raw wastewater, acid blue and aniline dyestuff clearance can reach more than 88%.
Embodiment three
Main containing anthraquinone dyes reactive brilliant bule and phenol in certain organic waste water, concentration is at about 1500mg/L, and the salinity in waste water is up to 12%, and the massfraction of mineral acid is 4%.Conventional Biochemical method is difficult to be effective.In the present invention, first this organic waste water is introduced and be equipped with DSA electrode pair and DSA-carbon dioxide process carbon electrode in the electrolyzer of the multiple combined type electrolysis reactor formed, control current density: 80 (A/m
2), voltage: 10v, electrolysis time: 10min.In electrolytic process, changing cathode and anode directions by changing set banister direction, thus analysing oxygen in altering reactor, analyse the carrying out of the electrolytic reactions such as chlorine.Along with the waste water that carries out of electrolysis fades gradually.Show that its structure changes, chromophoric group or auxochrome group are damaged.Spe membrane treatment system is introduced in electrolysis water outlet, and flow control is 60L/h, and temperature is room temperature.The mould material used is take polysulfone hollow fibre as the Polymethyl methacrylate tubular membrane of carrier, and membrane module is containing composite tube type spe membrane 400, and film bore is 1mm, thickness 0.1mm, and length is 1m.Above-mentioned composite tube type film epoxy sealing, in plexi-glass tubular, forms shell side and tube side.Respectively electrolysis water outlet is connected with shell side with the tube side of membrane module with activated sludge tank with pump, forms each self circular loop.Electrolysis wastewater enters tubular membrane inside, and in bio-reactor, supernatant liquor circulation enters shell side as back extraction phase.Small organic molecule then in waste water to be extracted and the larger molecular organics being difficult to degrade enter back extraction phase through film, mutually afterwards by being pumped into bio-reactor; The holding tank then entering recycling system from the internal passages of spe membrane pipe containing the waste water of acid ion, inorganic ion treats reuse.Bio-reactor volume is 500L, and sludge concentration is 7000mg/L, and regularly supplement the nutrients material, and be activated sludge aeration with pneumatic pump, Dissolved Oxygen concentration Control is at about 1.5mg/L.Combined electrolysis-extraction-biological treatment reactor of the present invention runs 1000h continuously, and in raw wastewater, reactive brilliant bule and phenol dyestuff clearance can reach more than 90%.
Embodiment four
Main containing azo dyes sun green and aniline in certain organic waste water, concentration is at about 3000mg/L, and the salinity in waste water is up to 16%, and the massfraction of mineral acid is 5%.Conventional Biochemical method is difficult to be effective.In the present invention, first this organic waste water is introduced and be equipped with DSA electrode pair and DSA-carbon dioxide process carbon electrode in the electrolyzer of the multiple combined type electrolysis reactor formed, control current density: 150 (A/m
2), voltage: 13v, electrolysis time: 18min.In electrolytic process, changing cathode and anode directions by changing set banister direction, thus analysing oxygen in altering reactor, analyse the carrying out of the electrolytic reactions such as chlorine.Along with the waste water that carries out of electrolysis fades gradually.Show that its structure changes, chromophoric group or auxochrome group are damaged.Spe membrane treatment system is introduced in electrolysis water outlet, and flow control is 70L/h, and temperature is room temperature.The mould material used is take polysulfone hollow fibre as the Polymethyl methacrylate tubular membrane of carrier, and membrane module is containing composite tube type spe membrane 480, and film bore is 1mm, thickness 0.1mm, and length is 1m.Above-mentioned composite tube type film epoxy sealing, in plexi-glass tubular, forms shell side and tube side.Respectively electrolysis water outlet is connected with shell side with the tube side of membrane module with activated sludge tank with pump, forms each self circular loop.Electrolysis wastewater enters tubular membrane inside, and in bio-reactor, supernatant liquor circulation enters shell side as back extraction phase.Small organic molecule then in waste water to be extracted and the larger molecular organics being difficult to degrade enter back extraction phase through film, mutually afterwards by being pumped into bio-reactor; The holding tank then entering recycling system from the internal passages of spe membrane pipe containing the waste water of acid ion, inorganic ion treats reuse.Bio-reactor volume is 500L, and sludge concentration is 7500mg/L, and regularly supplement the nutrients material, and be activated sludge aeration with pneumatic pump, Dissolved Oxygen concentration Control is at about 1.7mg/L.Combined electrolysis-extraction-biological treatment reactor of the present invention runs 1000h continuously, and in raw wastewater, direct brown and aniline dyestuff clearance can reach more than 91.5%.
In the embodiment of the present invention, the molecular formula of some dyes and structural formula are as shown in following table one:
The molecular formula of some dyes and structural formula in table one embodiment of the present invention
Claims (9)
1. a method for electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, is characterized in that:
1) organic waste water is carried out electrolysis by compound electric solution, obtain the waste water to be extracted comprising organic composition and inorganic components; Described organic waste water contains inorganic salt, mineral acid and macromole organic pollutant, and the massfraction of described inorganic salt is more than 1%; DSA electrode pair and DSA-carbon dioxide process carbon electrode is adopted to carry out electrolysis to the multiple combined type electrolysis reactor formed in described compound electric solution;
2) by step 1) waste water to be extracted that obtains to introduce in membrane extraction system and to be separated with inorganic components by organic composition;
3) step 2 is made) isolated organic composition enters biological treatment system and carries out biological degradation, until the water outlet of biological treatment system reaches emission standard, thus completes the process of high salt organic wastewater with difficult degradation thereby;
Described step 2) in membrane extraction system comprise the tube side that is made up of tubular silicon rubber diaphragm and the outer sheathed shell side of tube side; Waste water to be extracted is introduced into tube side internal cavities, organic composition wherein enters shell side through silicone rubber membrane membranous wall, enter biological treatment system through shell-side outlet again and carry out biological degradation, inorganic components is recycled from tube side internal cavities through tube side outlet discharge.
2. the method for a kind of electrolysis-perstraction according to claim 1-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, is characterized in that: described step 1) in macromole organic pollutant in organic waste water comprise aromatic organic compounds.
3. the method for a kind of electrolysis-perstraction according to claim 1-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, is characterized in that: described step 1) in the electrolytic condition that adopts of compound electric solution be: current density: 80 ~ 180A/m
2, voltage: 10 ~ 15V, electrolysis time: 10 ~ 20min.
4. the method for a kind of electrolysis-perstraction according to claim 1-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: described step 3) in the water outlet of biological treatment system enter shell side again through shell side inlet and use as the strip liquor of membrane extraction system, or rear discharge up to standard.
5. the method for a kind of electrolysis-perstraction according to claim 1 or 4-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: described biological treatment system comprises the biophase of taming in advance through organic waste water, described biophasic sludge concentration is 5000 ~ 8000mg/L, and Dissolved Oxygen concentration Control is at 1.5 ~ 2.0mg/L.
6. the device of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: comprise electrolyzer, membrane extraction system and biological treatment system, described electrolyzer comprises multiple combined type electrolysis reactor, multiple combined type electrolysis reactor by DSA electrode pair and DSA-carbon dioxide process carbon electrode to forming; Membrane extraction system comprises tube side and the outer sheathed shell side of tube side, and described tube side is the silicone rubber membrane of some tubular types, and the water side of electrolyzer is connected with silicone rubber membrane inlet end, and the exit end of silicone rubber membrane connects recycling system; The exit end of shell side connects the inlet end of biological treatment system, and the exit end of biological treatment system and the inlet end of shell side are connected to form loop, and the exit end of biological treatment system also connects blowdown system.
7. the device of a kind of electrolysis-perstraction according to claim 6-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: described DSA electrode is covered with paint, lacquer, colour wash, etc. rare elements or its oxide compound or titanyl compound and is prepared from titanium base, and described rare elements comprises tin, antimony or ruthenium.
8. the device of a kind of electrolysis-perstraction according to claim 6-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: adopt some to take polysulfone hollow fibre as polydimethylsiloxane tubular membrane or the Polymethyl methacrylate tubular membrane of carrier in described membrane extraction system, in plexi-glass tubular, form tube side and shell side by epoxy sealing.
9. the device of a kind of electrolysis-perstraction according to claim 6 or 8-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby, it is characterized in that: described silicone rubber membrane comprises 350 ~ 500, film bore is 1mm, thickness 0.1mm, and length is 1m.
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| CN105836847A (en) * | 2016-05-31 | 2016-08-10 | 陕西科技大学 | Device and method for stepwise extracting mixed organic matters in high-salinity wastewater by using combined membrane |
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