CN107176760A - A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system - Google Patents

A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system Download PDF

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CN107176760A
CN107176760A CN201710492441.1A CN201710492441A CN107176760A CN 107176760 A CN107176760 A CN 107176760A CN 201710492441 A CN201710492441 A CN 201710492441A CN 107176760 A CN107176760 A CN 107176760A
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cyanide
waste water
ammonia
high salt
cyanogen
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朱来松
孙阳
高占平
王皖蒙
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Nanjing Cec Environmental Protection Co Ltd
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Nanjing Cec Environmental Protection Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/20Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/18Cyanides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/002Construction details of the apparatus
    • C02F2201/007Modular design
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used

Abstract

The invention discloses a kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system, mainly metal zirconium production waste water is neutralized, except cyanogen, except ammonia nitrogen, except COD etc. is handled.Its technique is related to the group technologies such as coagulating sedimentation, ammonia aeration, electrochemistry/chemical oxidation, biochemical reaction, and device includes coagulative precipitation device, ammonia aeration device, electrolytically decomposing cyanide device, chemistry except treatment facilities such as cyanogen device, electrocatalysis oxidation apparatus, chemical oxidation device, water distribution hydrolytic tank, A/O biochemistry pools, second ponds.The present invention solves the processing problem of high salt, high cyanide, high COD and high ammonia nitrogen.Sewage treatment technology process is long, but each technique gives full play to feature, and specific aim removes each characteristic contamination, and operating cost is relatively low, and fundamentally removes the pollutants such as cyanogen, COD, ammonia nitrogen, and operational effect is stable.

Description

A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system
Technical field
The invention belongs to technical field of waste water processing, it is related to a kind of high salt advance for the treatment of process of cyanide-bearing effluent and device, especially fits The wastewater treatment produced for the Metal Production such as metal zirconium industry, belongs to environmental technology field.
Background technology
Cyanide (cyano-containing CN compound) is a kind of hypertoxic pollutant, plating, dyestuff, mining, metallurgy, petrochemical industry, Generally existing in the waste water that the industries such as coking are produced.Cyanide wastewater is directly discharged, and greatly danger can be caused to aquatiles such as fish Evil, destruction is ecological, in addition, cyanide wastewater can cause the agriculture underproduction, livestock dead, finally damages human health.
The harm that high-salt wastewater is caused to environment is especially big, especially the high-salt wastewater containing organic matter.High-salt wastewater is main From industries such as chemical industry, petrochemical industry, pharmacy.Highly salt containing organic waste water has to microorganism to be suppressed and toxic action, is mainly shown as Osmotic pressure causes microorganism dehydration to cause the raw matter separation of cell member, salting out to make enzymatic activity reduction etc..
Metal zirconium production waste water cyanide concentration is big, and total cyanogen is at concentrations up to 30000mg/L.Because concentration of cyanide is high, and Waste water is containing other to microorganism noxious material, it is impossible to carry out biochemical treatment direct to waste water, it is necessary to using broken cyanide processing.Both at home and abroad Conventional processing method containing cyanogen includes chloride oxidation method, electrochemical oxidation process, Ozonation, sulfur dioxide-air method etc., These method Treatment of Cyanide-containing Wastewater, which respectively have, achieves certain effect in advantage and disadvantage, engineering, but these methods have certain office Sex-limited, such as chloride oxidation method can produce substantial amounts of chlorine residue and other derivative products, cause secondary pollution, such as oxidizing process is to free Cyanide High treating effect, but it is general etc. to complex state cyanogen treatment effect.Metal zirconium production waste water cyanide concentration is high and contains complexing Cyanogen, intractability is big, cyanid can be made up to standard currently without preferable technique.Therefore research and development one kind can effectively go out always The processing of cyanogen and removal effect stable handling process and device to cyanide wastewater is significant.
Metal zirconium produces waste water mean salt amount 20000mg/L, belongs to high slat-containing wastewater.Highly salt containing organic waste water is mainly used Evaporation or dilution biochemical process.Not only equipment investment and operating cost are high for evaporation, evaporate the residue separated out generally as hazardous waste Disposal, is managed cumbersome, costly.Dilution biochemical process not only consumes freshwater resources, also increases the discharge volume of waste water, does not meet state Family's pollution emission reduction policy.
Metal zirconium production waste component is extremely complex, high containing cyanogen, high salt and COD, ammonia nitrogen concentration.At present, the country has no gold Belong to the Engineering Projects and report data of zirconium production wastewater treatment, but such waste water harmfulness is huge, if cannot effectively handle, Great problem of environmental pollution can be produced.Therefore, the processing problem of metal zirconium production production waste water is solved, it is useless to high salt class containing cyanogen The improvement of water has very important significance tool.
The content of the invention
Goal of the invention:In order to overcome the deficiencies in the prior art, the present invention provides a kind of high salt cyanide wastewater processing Technique and processing system, technique fully combine coagulating sedimentation, ammonia aeration, electrochemistry, chemical oxidation and biochemical reaction, using each From process characteristic, each characteristic contamination is targetedly removed, the processing for solving high salt, high cyanide, high COD and high ammonia nitrogen is difficult Topic.Even if complex treatment process, but operating cost is relatively low, and fundamentally remove the pollutants such as cyanogen, COD, ammonia nitrogen, operation Effect stability.
Technical scheme:To achieve the above object, the technical solution adopted by the present invention is:
A kind of high salt advance for the treatment of process of cyanide-bearing effluent, by coagulation-settlement process, ammonia aeration technique, electrochemical process, chemical oxygen Chemical industry skill and biochemical reaction technique are fully combined, using respective process characteristic and between influence each other, remove each feature dirty Contaminate thing.
The coagulation-settlement process is as follows:Feeding lime, coagulant and flocculation aid in coagulative precipitation tank, with to wastewater pH It is worth coarse adjustment, improves the adsorption effect to organic pollution, waste water suspension is removed by coagulant and flocculation aid;
The ammonia aeration technique is as follows:Ammonia nitrogen generally has two kinds of existence forms in water:NH4 +, NH3, under alkaline environment Following reaction forward is carried out:NH4 ++OH-→NH3+H2O, plus alkali make ammonia radical ion be converted into ammonia, then by being largely aerated, Promote NH3It is delivered in gas phase and is taken away by liquid phase, so as to reaches the purpose for removing ammonia nitrogen;
The electrochemical process is as follows:Cyanide wastewater in a cell, in the basic conditions, CN- is easy to electrochemical Learn oxidation;In oxidation reaction process, CN- is oxidized to cyanic acid ion first, as shown in 1. formula, then cyanic acid ion water Solution generation ammonia and carbanion, as shown in 2. formula, at the same time, cyanic acid ion can also continue oxidation, produce CO2And N2, such as 3. shown in formula:
CN+2OH—2e-→CNO+H2O ①
CNO+2H2O→NH4 ++CO3 2—
2CNO+4OH—6e-→2CO2↑+N2↑+2H2O ③
Chemical broken cyanide principle:Using HClO strong oxidizing property broken cyanide, reaction equation is as follows when pH is more than 10:
CN-+HClO→CNCl+OH-
CNCl+2OH-→CNO-+Cl-+H2O
PH reaction equations in neutral and acidity are as follows:
2CNO+3ClO+2H+→2CO2↑+N2↑+3Cl+H2O;
Chemical oxidation process is Electrocatalytic Oxidation, specific as follows:Electrocatalytic Oxidation be using anode high potential or Hydroxyl radical free radical produced by anode reaction, by the pollutant oxidative degradation in waste water so as to reach the method for removal:
Fe2++H2O2→Fe3++·OH+OH-
Fe3++H2O2·→Fe2++O2+2H+
Fe3++O2→Fe2++·O2
The biochemical reaction technique include hydrolysis acidification technique and A/O techniques, wherein hydrolysis acidification technique by hydrolyze bacterium, The enzymatic of acid-producing bacteria release makes to be difficult to biodegradable macromolecular substances generation biocatalytic reaction in water, is embodied in chain rupture With it is water-soluble;A dissolved matter part in liquid phase is absorbed in hydrolytic tank by bacterium, is converted into energy and CO2、NH3Deng Metabolite, another part will be handled into the follow-up Aerobic biological process stage with current by aerobic bacteria metabolism;
A/O techniques be utilize anaerobic-aerobic tandem process, denitrification-nitration reaction is constantly carried out, by BOD remove with Anoxic/aerobic system that denitrification denitrogenation is completed in same pond;Anoxic pond is carried out with anti-nitre using heterotroph aerobic-anaerobic microbe Change, remove the total nitrogen and organic matter in sewage;Aerobic Pond is nitrified and decarburizing reaction.
A kind of high salt cyanide-containing waste water treatment system, including the regulating reservoir (1), coagulative precipitation device (2), the ammonia that are sequentially communicated blow De- device (3), electrolytically decomposing cyanide device (4), chemistry except cyanogen device (5), electrocatalysis oxidation apparatus (6), chemical oxidation device (7), Physico-chemical precipitation pond (8), water distribution hydrolytic tank (9), A/O biochemistry pools (10), second pond (11), discharge bay (12).
It is preferred that:Also include sludge-tank, the coagulative precipitation device (2), physico-chemical precipitation pond (8), second pond (11) and dirt Mud sump is connected.
It is preferred that:The lime that the coagulative precipitation device (2) includes being sequentially communicated puts into area, coagulant input area and helped Solidifying agent input area;The coagulative precipitation device (2) include coagulating sedimentation shell, the first upper spacer, the second upper spacer, first under every Plate, the second lower clapboard, first upper spacer, the second upper spacer are arranged at coagulating sedimentation cover top portion, and the first lower clapboard, Two lower clapboards are arranged at coagulating sedimentation outer casing bottom, and first upper spacer and the pairing of the first lower clapboard are set, and form current Passage one;And second upper spacer and the pairing of the second lower clapboard are set, water stream channel two is formed;Wherein, the first upper spacer, Coagulating sedimentation enclosure region is divided on lime input area, the first upper spacer, the first lower clapboard and second by one lower clapboard Coagulating sedimentation enclosure region is divided into coagulant input area by dividing plate, the second lower clapboard;Second upper spacer, the second lower clapboard will Coagulating sedimentation enclosure region is divided into flocculation aid input area;The coagulative precipitation device (2) adds medicament and is respectively lime, mixes Solidifying agent and flocculation aid, pH value are controlled between 8.0-9.0, and coagulative precipitation device (2) goes out aqueous suspension less than 20mg/L.
It is preferred that:The ammonia aeration device (3) includes liquid caustic soda mixing pit, aeration tower, the ammonia absorber being sequentially connected, described Waste water circulation unit is provided between liquid caustic soda mixing pit, aeration tower;Ammonia aeration device (3) the water outlet ammonia nitrogen concentration is less than 200mg/L。
It is preferred that:Electrolytically decomposing cyanide device (4) is respectively provided with to complex cyanide and free Cyanide efficiently abolishes function, total cyanogen clearance Up to more than 95%.
It is preferred that:Chemistry reacts progress in two stages except cyanogen device (5), and pH value in reaction is controlled 10 or so with respectively Property, medicament is added for sodium hypochlorite.
It is preferred that:Water distribution hydrolytic tank (9) residence time, sanitary sewage water distribution multiplying power was in 4-5 times, water distribution water in more than 36h Xie Chi (9) water outlet TDS is controlled in below 6000mg/L;A/O biochemistry pools (10) effluent COD concentration is less than 450mg/L, ammonia nitrogen concentration Less than 40mg/L.
It is preferred that:High salt cyanide wastewater removes cyanogen process by electrolytically decomposing cyanide device (4) and chemistry except cyanogen device (5) is combined, Total cyanogen content is down to below 100mg/L from 20000mg/L;Electrocatalysis oxidation apparatus (6) and chemical oxidation device (7) joint drop Low waste water COD, the catalyst produced using electrocatalysis oxidation apparatus (6), chemical oxidation device (7) only needs to add hydrogen peroxide oxidation Agent can ensure effectively to remove COD effects;High salt cyanide wastewater is through electrocatalysis oxidation apparatus (6) and chemical oxidation device (7) place COD is down to below 10000mg/L after reason.
The present invention compared with prior art, has the advantages that:
The present invention solves the processing problem of high salt, high cyanide, high COD and high ammonia nitrogen.Sewage treatment technology process is long, But operating cost is relatively low, and the pollutants such as total cyanogen, COD, ammonia nitrogen are fundamentally removed, operational effect is stable, can effectively locate Manage metal zirconium high salt cyanide wastewater.
Brief description of the drawings
Accompanying drawing 1 is process flow diagram of the invention.
Regulating reservoir 1, coagulative precipitation device 2 system process figure of the accompanying drawing 2 for the present invention.
Accompanying drawing 3 is the system process figure of ammonia aeration device 3 of the invention.
Accompanying drawing 4 is the system process figure of electrolytically decomposing cyanide device 4 of the invention.
Accompanying drawing 5 removes the system process figure of cyanogen device 5 for the chemistry of the present invention.
Accompanying drawing 6 is the system process figure of electrocatalysis oxidation apparatus 6 of the invention.
Accompanying drawing 7 is chemical oxidation device 7 and the system process figure of physico-chemical precipitation pond 8 of the invention.
Accompanying drawing 8 is the water distribution hydrolytic tank 9 of the present invention, A/O biochemistry pools 10, second pond 11, the system process of discharge bay 12 Figure.
In figure:1-regulating reservoir, 2-coagulative precipitation device, 3-ammonia aeration device, 4-electrolytically decomposing cyanide device, 5-chemistry Except cyanogen device, 6-electrocatalysis oxidation apparatus, 7-chemical oxidation device, 8-physico-chemical precipitation pond, 9-water distribution hydrolytic tank, 10-A/ O biochemistry pools, 11-second pond, 12-discharge bay.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is furture elucidated, it should be understood that these examples are merely to illustrate this Invention rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are various to the present invention's The modification of the equivalent form of value falls within the application appended claims limited range.
A kind of high salt advance for the treatment of process of cyanide-bearing effluent, as shown in figure 1, by coagulating sedimentation, ammonia aeration, electrochemistry, chemical oxidation Fully combined with biochemical reaction technique, using respective process characteristic, targetedly remove each characteristic contamination, solve high salt, The processing problem of high cyanide, high COD and high ammonia nitrogen.Even if complex treatment process, but operating cost is relatively low, and from basic The pollutants such as upper removal cyanogen, COD, ammonia nitrogen, operational effect is stable.
(1) coagulating sedimentation:Coagulating sedimentation feeding lime, coagulant and flocculation aid.Waste water contains a certain amount of suspension, is Ensure the operation of follow-up ammonia aeration device, it is necessary to be removed to suspension.Lime is used for pH value of waste water coarse adjustment, improves to organic The adsorption effect of pollutant, while being prepared for ammonia aeration technique, coagulant and flocculation aid improve and waste water suspension are gone Except effect.
(2) ammonia aeration:Ammonia nitrogen generally has two kinds of existence forms in water:NH4 +, NH3, it is following under alkaline environment to react just To progress:NH4 ++OH-→NH3+H2O, therefore add alkali ammonia radical ion is converted into ammonia,.By being largely aerated, promote NH3By liquid Mutually it is delivered in gas phase and takes away, so that the purpose for removing ammonia nitrogen is reached, due to passing through the coarse adjustment of lime from coagulating sedimentation water, During ammonia aeration technique, in the accurate adjustment by adding alkali so that NH4 +, NH3, it is alkaline more accurate that forward direction is reacted, after aeration NH3The amount for becoming gas phase is bigger.
(3) broken cyanide:It is divided into electrolytically decomposing cyanide and chemistry removes cyanogen.
Electrolytically decomposing cyanide principle of device:Cyanide wastewater in a cell, in the basic conditions, CN- is easy to by electrochemistry Oxidation.In oxidation reaction process, CN- is oxidized to cyanic acid ion (1. formula) first, then cyanic acid ion hydrolysis generation Ammonia (volatilization) and carbanion (2. formula), at the same time, cyanic acid ion can also continue oxidation, produce CO2And N2(3. formula).
CN+2OH—2e-→CNO+H2O ①
CNO+2H2O→NH4 ++CO3 2—
2CNO+4OH—6e-→2CO2↑+N2↑+2H2O ③
Chemical broken cyanide principle:Using HClO strong oxidizing property broken cyanide, reaction equation is as follows when pH is more than 10:
CN-+HClO→CNCl+OH-
CNCl+2OH-→CNO-+Cl-+H2O
PH reaction equations in neutral and acidity are as follows:
2CNO+3ClO+2H+→2CO2↑+N2↑+3Cl+H2O
Add the accurate adjustment of alkali due to passing through from the water of ammonia aeration technique so that electrochemical oxidation cyanogen breaking process is in alkali Property environment in, beneficial to the processing of electrochemical oxidation technique, after electrochemical oxidation PROCESS FOR TREATMENT, due to liquid or alkalescence, It can directly utilize HClO strong oxidizing property broken cyanide, after alkaline environment HClO broken cyanides, sulfuric acid neutralising fluid alkalescence will be entered so that Liquid shows neutral, adds sodium hypochlorite separation of nitrogen.
(4) aoxidize:It is divided into electrocatalytic oxidation and chemical oxidation.
Electrocatalytic Oxidation is as a kind of high-level oxidation technology, with oxidability is strong, reaction speed is fast and without secondary dirt The advantages of dye, electrocatalytic oxidation is using the hydroxyl radical free radical produced by the high potential or anode reaction of anode, by waste water Pollutant oxidative degradation so as to reaching the method for removal.
Chemical oxidation refers to utilize the hydroxyl radical free radical produced in chemical reaction process, organic matter is thoroughly decomposed or part Decompose and remove.Compared with common oxidizing process, the maximum feature of advanced oxidation processes is:Produce a large amount of very active hydroxyl frees Base OH, reaction rate is faster, more efficient, and non-selectivity.
Fe2++H2O2→Fe3++·OH+OH-
Fe3++H2O2·→Fe2++O2+2H+
Fe3++O2→Fe2++·O2
(5) it is biochemical:Including hydrolysis acidification and A/O techniques.
Hydrolysis acidification makes to be difficult to biodegradable macromolecular substances generation in water by hydrolyzing the enzymatic that bacterium, acid-producing bacteria discharge Biocatalytic reaction, is embodied in chain rupture and water-soluble, so that the biodegradability and degradation speed of waste water are increased substantially.Liquid A dissolved matter part in phase is absorbed in hydrolytic tank by bacterium, is converted into energy and CO2、NH3Deng metabolite, Another part will be handled into the follow-up Aerobic biological process stage with current by aerobic bacteria metabolism.
A/O techniques be utilize anaerobic-aerobic tandem process, denitrification-nitration reaction is constantly carried out, by BOD remove with Anoxic/aerobic system that denitrification denitrogenation is completed in same pond.Anoxic pond is carried out with anti-nitre using heterotroph aerobic-anaerobic microbe Change, remove the total nitrogen and organic matter in sewage.Aerobic Pond is nitrified and decarburizing reaction.
A kind of high salt cyanide-containing waste water treatment system, as shown in figure 1, including the regulating reservoir 1, the coagulative precipitation device that are sequentially communicated 2nd, ammonia aeration device 3, electrolytically decomposing cyanide device 4, chemistry remove cyanogen device 5, electrocatalysis oxidation apparatus 6, chemical oxidation device 7, materialization Sedimentation basin 8, water distribution hydrolytic tank 9, A/O biochemistry pools 10, second pond 11, discharge bay 12 and sludge-tank.The coagulative precipitation device 2nd, physico-chemical precipitation pond 8, second pond 11 are connected with sludge-tank.
As shown in Figure 2:The coagulative precipitation device 2 include be sequentially communicated lime input area, coagulant input area and Flocculation aid puts into area;The coagulative precipitation device 2 include coagulating sedimentation shell, the first upper spacer, the second upper spacer, first under every Plate, the second lower clapboard, first upper spacer, the second upper spacer are arranged at coagulating sedimentation cover top portion, and the first lower clapboard, Two lower clapboards are arranged at coagulating sedimentation outer casing bottom, and first upper spacer and the pairing of the first lower clapboard are set, and form current Passage one;And second upper spacer and the pairing of the second lower clapboard are set, water stream channel two is formed;Wherein, the first upper spacer, Coagulating sedimentation enclosure region is divided on lime input area, the first upper spacer, the first lower clapboard and second by one lower clapboard Coagulating sedimentation enclosure region is divided into coagulant input area by dividing plate, the second lower clapboard;Second upper spacer, the second lower clapboard will Coagulating sedimentation enclosure region is divided into flocculation aid input area;It is respectively lime, coagulation that the coagulative precipitation device 2, which adds medicament, Agent and flocculation aid, pH value are controlled between 8.0-9.0, and coagulative precipitation device 2 goes out aqueous suspension less than 20mg/L, it is ensured that ammonia aeration Device 3 is normally run.
As shown in Figure 3:The ammonia aeration device 3 includes liquid caustic soda mixing pit, aeration tower, the ammonia absorber being sequentially connected, institute State and waste water circulation unit is provided between liquid caustic soda mixing pit, aeration tower;The water outlet ammonia nitrogen concentration of ammonia aeration device 3 is less than 200mg/L。
As shown in Figure 4:For electrolytically decomposing cyanide device 4, complex cyanide and free Cyanide are respectively provided with and efficiently abolish function, total cyanogen is gone Except rate is up to more than 95%.
As shown in Figure 5:Chemistry reacts progress in two stages except cyanogen device 5, and pH value in reaction is controlled 10 or so with respectively Property, medicament is added for sodium hypochlorite.
As shown in figs 6-8:The residence time of water distribution hydrolytic tank 9, sanitary sewage water distribution multiplying power was in 4-5 times, water distribution in more than 36h The water outlet TDS of hydrolytic tank 9 is controlled in below 6000mg/L;The effluent COD concentration of A/O biochemistry pools 10 is less than 450mg/L, and ammonia nitrogen concentration is low In 40mg/L.High salt cyanide wastewater removes cyanogen process by electrolytically decomposing cyanide device 4 and chemistry except cyanogen device 5 is combined, by total cyanogen content Below 100mg/L is down to from 20000mg/L;Electrocatalysis oxidation apparatus 6 and the joint reduction waste water COD of chemical oxidation device 7, are utilized The catalyst that electrocatalysis oxidation apparatus 6 is produced, chemical oxidation device 7, which only needs to add hydrogen peroxide oxidant, can ensure effectively to remove COD effects;After high salt cyanide wastewater is handled through electrocatalysis oxidation apparatus 6 and chemical oxidation device 7 COD be down to 10000mg/L with Under.
When it is implemented, handling process mainly includes following several stages:
(1) waste water is through pipeline to regulating reservoir 1, and boosted pump is promoted to coagulative precipitation device 2.Elevator pump sets waste water Return duct, is well mixed to regulating reservoir waste water.The feeding lime of coagulative precipitation device 2, coagulant and flocculation aid, in waste water SS and colloid type organic be removed, reduce the difficulty of subsequent treatment, it is to avoid the dirt of ammonia aeration device 3 is blocked up.Coagulating sedimentation Device 2 sets sludge delivery pump, and sludge periodically is delivered into sludge-tank.
(2) water outlet of coagulative precipitation device 2 gravity flow flows into ammonia aeration intermediate pool, adds liquid caustic soda adjustment wastewater pH and is more than 11, Molecules of ammonia most in waste water are removed through ammonia aeration device 3, ammonia is through sulfuric acid absorption, it is to avoid secondary pollution.
(3) water outlet of ammonia aeration device 3 is discharged into electrolytically decomposing cyanide device 4 and carries out broken cyanide processing, and electrolytically decomposing cyanide need not adjust useless Water pH value.Water outlet enters chemistry except cyanogen device 5 after electrolytically decomposing cyanide, and cyanogen is further removed using oxidant.Chemistry is divided to two sections to enter except cyanogen OK, first paragraph is to carry out in the basic conditions, and second segment carries out thoroughly removing cyanogen under neutral environment.
(4) chemistry is except the water outlet of cyanogen device 5 is into the progress of electrocatalysis oxidation apparatus 6 COD degraded removal, and water outlet enters chemistry Oxidation unit 7, COD in waste water is further removed by adding hydrogen peroxide.The water outlet of chemical oxidation device 7 adds liquid caustic soda and helps solidifying Agent, subsequent biochemical system is discharged into through the supernatants after precipitation of physico-chemical precipitation pond 8.The sludge that physico-chemical precipitation pond 8 is produced is conveyed by sludge Pump is delivered to sludge-tank.
(5) metal zirconium high salt production waste water containing cyanogen is discharged into water distribution hydrolytic tank 9 after above-mentioned pretreatment, while collecting plant area Sanitary sewage is used for the salinity for diluting waste water, it is ensured that the normal operation of biochemical treatment system.Set and fill out in water water distribution hydrolytic tank 9 Material, loads substantial amounts of microorganism, improves the adaptability to the impact load of waste water, waste water is further improved by hydrolysis Biodegradability.Waste water after water distribution and hydrolysis is promoted to A/O reaction tanks 10 through pump.Waste water is in anoxic A ponds and the activity of backflow Diving mixer is set in sludge and nitrification liquid mixing, anoxic A ponds, is carried out with denitrification, gone using heterotroph aerobic-anaerobic microbe Except the total nitrogen and organic matter in sewage.Aerobic O ponds carry out biochemical treatment using aerobic microbiological, and carbonaceous organic material in sewage is entered Row is degraded and the ammonia nitrogen in sewage is nitrified.From aerobic O ponds, gravity flow enters second pond 11 to waste water, and 11 pairs of biochemistry of second pond go out Water carries out separation of solid and liquid, and supernatant is discharged into discharge bay 12, after testing qualified rear standard discharge.The partial sludge blowback of second pond 11 Anoxic A ponds are flow to, excess sludge drains into sludge-tank.High salt advance for the treatment of process of cyanide-bearing effluent and device solve high salt, high cyanide, High COD and high ammonia nitrogen processing problem.Waste water treatment process is long, but each technique gives full play to feature, and specific aim removes each feature Pollutant, operating cost is relatively low, and fundamentally removes the pollutants such as cyanogen, COD, ammonia nitrogen, and operational effect is stable.
Described above is only the preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of high salt advance for the treatment of process of cyanide-bearing effluent, it is characterised in that:By coagulation-settlement process, ammonia aeration technique, electrochemistry work Skill, chemical oxidation process and biochemical reaction technique are fully combined, using respective process characteristic and between influence each other, remove Each characteristic contamination.
2. high salt advance for the treatment of process of cyanide-bearing effluent according to claim 1, it is characterised in that:The coagulation-settlement process is as follows: Feeding lime, coagulant and flocculation aid in coagulative precipitation tank, to pH value of waste water coarse adjustment, to improve the absorption to organic pollution Effect, waste water suspension is removed by coagulant and flocculation aid;
The ammonia aeration technique is as follows:Ammonia nitrogen generally has two kinds of existence forms in water:NH4 +, NH3, it is following under alkaline environment Reaction forward is carried out:NH4 ++OH-→NH3+H2O, plus alkali make ammonia radical ion be converted into ammonia, then by being largely aerated, promote NH3It is delivered in gas phase and is taken away by liquid phase, so as to reaches the purpose for removing ammonia nitrogen;
The electrochemical process is as follows:Cyanide wastewater in a cell, in the basic conditions, CN- is easy to by electrochemistry oxygen Change;In oxidation reaction process, CN- is oxidized to cyanic acid ion first, as shown in 1. formula, then cyanic acid ion hydrolysis life Ammonification and carbanion, as shown in 2. formula, at the same time, cyanic acid ion can also continue oxidation, produce CO2And N2, such as 3. formula It is shown:
CN+2OH—2e-→CNO+H2O ①
CNO+2H2O→NH4 ++CO3 2—
2CNO+4OH—6e-→2CO2↑+N2↑+2H2O ③
Chemical broken cyanide principle:Using HClO strong oxidizing property broken cyanide, reaction equation is as follows when pH is more than 10:
CN-+HClO→CNCl+OH-
CNCl+2OH-→CNO-+Cl-+H2O
PH reaction equations in neutral and acidity are as follows:
2CNO+3ClO+2H+→2CO2↑+N2↑+3Cl+H2O;
Chemical oxidation process is Electrocatalytic Oxidation, specific as follows:Electrocatalytic Oxidation is the high potential or anode using anode Hydroxyl radical free radical produced by reaction, by the pollutant oxidative degradation in waste water so as to reach the method for removal:
Fe2++H2O2→Fe3++·OH+OH-
Fe3++H2O2·→Fe2++O2+2H+
Fe3++O2→Fe2++·O2
The biochemical reaction technique includes hydrolysis acidification technique and A/O techniques, and wherein hydrolysis acidification technique is by hydrolyzing bacterium, production acid The enzymatic of bacterium release makes to be difficult to biodegradable macromolecular substances generation biocatalytic reaction in water, is embodied in chain rupture and water It is molten;A dissolved matter part in liquid phase is absorbed in hydrolytic tank by bacterium, is converted into energy and CO2、NH3Deng metabolism Product, another part will be handled into the follow-up Aerobic biological process stage with current by aerobic bacteria metabolism;
A/O techniques are to utilize anaerobic-aerobic tandem process, denitrification-nitration reaction is constantly carried out, and BOD is removed and anti-nitre Change anoxic/aerobic system that denitrogenation is completed in same pond;Anoxic pond is carried out with denitrification using heterotroph aerobic-anaerobic microbe, is gone Except the total nitrogen and organic matter in sewage;Aerobic Pond is nitrified and decarburizing reaction.
3. a kind of high salt cyanide-containing waste water treatment system, it is characterised in that:Including regulating reservoir (1), the coagulating sedimentation dress being sequentially communicated (2), ammonia aeration device (3), electrolytically decomposing cyanide device (4), chemistry are put except cyanogen device (5), electrocatalysis oxidation apparatus (6), chemical oxygen (7), physico-chemical precipitation pond (8), water distribution hydrolytic tank (9), A/O biochemistry pools (10), second pond (11), discharge bay (12) are put in makeup.
4. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:Also include sludge-tank, the coagulation Settler (2), physico-chemical precipitation pond (8), second pond (11) are connected with sludge-tank.
5. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:Coagulative precipitation device (2) bag Include the lime input area being sequentially communicated, coagulant input area and flocculation aid input area;The coagulative precipitation device (2) includes mixed Retrogradation shallow lake shell, the first upper spacer, the second upper spacer, the first lower clapboard, the second lower clapboard, first upper spacer, on second Dividing plate is arranged at coagulating sedimentation cover top portion, and the first lower clapboard, the second lower clapboard are arranged at coagulating sedimentation outer casing bottom, and institute State the first upper spacer and the pairing of the first lower clapboard is set, form water stream channel one;And second upper spacer and the second lower clapboard Pairing is set, and forms water stream channel two;Wherein, coagulating sedimentation enclosure region is divided into by the first upper spacer, the first lower clapboard Lime puts into area, and the first upper spacer, the first lower clapboard and the second upper spacer, the second lower clapboard are by coagulating sedimentation enclosure area Domain is divided into coagulant input area;Coagulating sedimentation enclosure region is divided into flocculation aid input by the second upper spacer, the second lower clapboard Area;It is respectively lime, coagulant and flocculation aid that the coagulative precipitation device (2), which adds medicament, pH value control 8.0-9.0 it Between, coagulative precipitation device (2) goes out aqueous suspension less than 20mg/L.
6. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:The ammonia aeration device (3) includes Liquid caustic soda mixing pit, aeration tower, the ammonia absorber being sequentially connected, waste water circulation is provided between the liquid caustic soda mixing pit, aeration tower Unit;Ammonia aeration device (3) the water outlet ammonia nitrogen concentration is less than 200mg/L.
7. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:Electrolytically decomposing cyanide device (4) is to complexing Cyanogen and free Cyanide, which are respectively provided with, efficiently abolishes function, and total cyanogen clearance is up to more than 95%.
8. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:Chemistry is divided to two ranks except cyanogen device (5) Duan Fanying is carried out, and pH value in reaction is controlled in 10 or so and neutrality respectively, adds medicament for sodium hypochlorite.
9. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:Water distribution hydrolytic tank (9) residence time In more than 36h, sanitary sewage water distribution multiplying power is at 4-5 times, and water distribution hydrolytic tank (9) water outlet TDS is controlled in below 6000mg/L;A/O Biochemistry pool (10) effluent COD concentration is less than 450mg/L, and ammonia nitrogen concentration is less than 40mg/L.
10. high salt cyanide-containing waste water treatment system according to claim 3, it is characterised in that:High salt cyanide wastewater passes through electrolysis Broken cyanide device (4) and chemistry except cyanogen device (5) combination remove cyanogen process, by total cyanogen content from 20000mg/L be down to 100mg/L with Under;Electrocatalysis oxidation apparatus (6) and chemical oxidation device (7) joint reduction waste water COD, are produced using electrocatalysis oxidation apparatus (6) Raw catalyst, chemical oxidation device (7), which only needs to add hydrogen peroxide oxidant, can ensure effectively to remove COD effects;High salt contains Cyanogen waste water COD after electrocatalysis oxidation apparatus (6) and chemical oxidation device (7) processing is down to below 10000mg/L.
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CN111977900A (en) * 2020-08-17 2020-11-24 山东绿创环境科技有限公司 Coal-based urea production wastewater treatment process, system and application
CN112266129A (en) * 2020-09-29 2021-01-26 武汉大学 Wastewater treatment apparatus and wastewater treatment method
CN112279457A (en) * 2020-10-15 2021-01-29 泉州南京大学环保产业研究院 Caprolactam comprehensive wastewater treatment device and treatment method thereof
CN113213656A (en) * 2021-03-23 2021-08-06 高和平 Novel system for treating coking wastewater by catalytic oxidation method
CN114275906A (en) * 2021-12-10 2022-04-05 安徽安泰农业开发有限责任公司 Composite microbial inoculum for treating sewage of pig farm and preparation method thereof
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CN115504620A (en) * 2022-05-30 2022-12-23 重庆大学 Preserved szechuan pickle wastewater treatment process based on water pollutant discharge standard of preserved szechuan pickle industry

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CN107487953A (en) * 2017-09-22 2017-12-19 长春黄金研究院 A kind of high-efficiency pretreatment method of high concentration waste water from dyestuff containing cyanogen
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CN110467307A (en) * 2018-05-09 2019-11-19 上海化学工业区中法水务发展有限公司 Wastewater from chemical industry electroxidation processing method with high salt
CN109574378A (en) * 2018-11-21 2019-04-05 河海大学 A kind of low cost agricultural chemicals waste water processing optimization technique
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CN112279457A (en) * 2020-10-15 2021-01-29 泉州南京大学环保产业研究院 Caprolactam comprehensive wastewater treatment device and treatment method thereof
CN113213656A (en) * 2021-03-23 2021-08-06 高和平 Novel system for treating coking wastewater by catalytic oxidation method
CN114275906A (en) * 2021-12-10 2022-04-05 安徽安泰农业开发有限责任公司 Composite microbial inoculum for treating sewage of pig farm and preparation method thereof
CN114778761A (en) * 2022-04-20 2022-07-22 西安近代化学研究所 QPQ process radical cyanate content determination device and method
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CN115504620A (en) * 2022-05-30 2022-12-23 重庆大学 Preserved szechuan pickle wastewater treatment process based on water pollutant discharge standard of preserved szechuan pickle industry

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Application publication date: 20170919