CN107487966A - A kind of coking distilled ammonia wastewater deep treatment method - Google Patents

A kind of coking distilled ammonia wastewater deep treatment method Download PDF

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CN107487966A
CN107487966A CN201710929839.7A CN201710929839A CN107487966A CN 107487966 A CN107487966 A CN 107487966A CN 201710929839 A CN201710929839 A CN 201710929839A CN 107487966 A CN107487966 A CN 107487966A
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water
demulsification
value
minutes
electrolysis
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代春龙
邹宗海
魏明勇
阚传金
孙垂刚
高庆刚
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Shandong Longantai Environmental Protection Sci-Tech Co Ltd
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Shandong Longantai Environmental Protection Sci-Tech Co Ltd
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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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes

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Abstract

A kind of coking distilled ammonia wastewater deep treatment method, including following processing step：A. by the demulsification of the coal tar of emulsification state, form the Production Wastewater By Combined Acidification And Demulsification step of suspension, for the control of acidifying solution pH value 1.5 3.5, the demulsification time is 13 hours；B. promote coal tar to separate out and aoxidize the phenols for being dissolved in water and the ozone pre-oxidation step of cyanogen class material；C. the air supporting step separated the coal tar after demulsification and water；D. the secondary filter step of two dephenolize oil removings；E. to the light electrolysis step of organic matter open loop chain rupture while removal partial organic substances, it is 23 to enter water management water inlet pH value, and it is 34 to go out water management pH value, and the light electrolysis time is 15 120 minutes；F. Fenton oxidation step；G. the anoxic removed/aerobic biochemical step；H. the catalytic and oxidative electrolysis technology step of advanced treating is carried out to organic matter and ammonia nitrogen.Treatment effect can reach《Integrated wastewater discharge standard》To the concentration of emission limit value requirement of COD, ammonia nitrogen, total nitrogen index in GB8978 1996.

Description

A kind of coking distilled ammonia wastewater deep treatment method
Technical field
It is biochemical+aerobic using materialized pretreatment+anoxic more particularly, to one kind the present invention relates to technical field of waste water processing Reuse method after biochemistry+catalytic and oxidative electrolysis technology depth.
Background technology
Coking chemical waste water be coking, coal gas in high-temperature retorting, purification and byproduct removal process, produce containing volatile phenol, The industrial wastewater of the heterocyclic compound such as polycyclic aromatic hydrocarbon and oxygen, sulphur, nitrogen is a kind of high CODcr, high phenol value, high ammonia nitrogen and is difficult place A kind of industrial organic waste water of reason.Its main source has three：First, remained ammonia, it is produced in the dry distillation of coal and coal gas cooling Born waste water, its water account for more than half of coking chemical waste water total amount, are the main sources of coking chemical waste water；It is second, net in coal gas The waste water generated during change, such as gas end-cooling water and crude benzol separation water；Third, in the subtractive processes such as tar, crude benzol And waste water caused by other occasions.Coking chemical waste water is the industrial wastewater containing a large amount of persistent organic pollutants, its complicated component, Containing poisonous and harmful substances such as substantial amounts of phenol, cyanogen, benzene, ammonia nitrogens, the coking chemical waste water of discharge beyond standards causes serious pollution to environment. Coking chemical waste water have water quality and quantity change greatly, complicated component, organic matter particularly hardly degraded organic substance content is high, ammonia nitrogen concentration height The features such as.Nitrogen-containing compound is organic matter large number of in Coking Plant Wastewater and that composition is sufficiently complex.The quinoline that mass spectrograph is made Quinoline and some alkyl substituents, are suspected of carcinogen.Aromatic hydrocarbons and aromatic amine etc. equally have many bioactive substances.Phthalandione vinegar Class is another kind of carcinogen in waste water, and dimethyl phthalate therein, phthalandione di-isooctyl are also that EPA is preferentially detected Pollutant.In a word, the complicated component of coking chemical waste water, pollutant kind is various, wherein much belonging to the life for having carcinogenic mutagenesis Active substances.For such phenol cyanogen class waste water, country does not allow directly to discharge.So coal chemical enterprise mostly returns this waste water For reuse after processing.
Coking waste water reuse precondition after processing must be meet it is up to standard, then further according to recycle-water requirement, consider Whether other handling process are used.For the index of recycle-water, the coke-oven plant of integrated iron and steel works, coal tar integrated complex, independence Coke-oven plant is distinguishing, and is also distinguishing using the coke-oven plant of wet quenching or CDQ.Realize coking chemical waste water Zero-emission, corresponding handling process need to be used to different reuse users according to enterprise nature, provide coking chemical waste water after processing Source obtains rationally utilizing to greatest extent.1. integrated iron and steel works, coking chemical waste water may be used also in addition to being back to coke-oven plant after processing For in iron and steel enterprise's turbid circulating water system.So wastewater treatment just needs to reach GBl3456-92《Steel and iron industry pollutant Discharge standard》In primary standard.2. coal tar integrated complex, coking chemical waste water can also be sent in addition to available for coke-oven plant after processing Toward coal washery, water is supplemented as coal washing, needs also exist for reaching GB8978-1996《Integrated wastewater discharge standard》In one-level mark It is accurate.3. independent coke-oven plant, if using wet quenching technique, coking chemical waste water should reach GB8978-1996 after processing《Sewage Comprehensive discharge standard》In primary standard.4. independent coke-oven plant, if using CDQ technique, while environmental administration is again not Allow outer row, even if not considering other waters, only distilled ammonia wastewater one is inconsumable in itself by coke-oven plant.It must use Advanced treatment process.
5. it is required that zero-emission, is only to consume the coking chemical waste water after processing in itself by coke-oven plant, it is necessary to using advanced treating Technique, the production water of advanced treating is set to be used to produce net circulating water supplement water.
The processing technological flow of existing coking distilled ammonia wastewater is mostly air supporting-A/O biochemistry, and water outlet COD is in 200-500mg/ L.The reason for PROCESS FOR TREATMENT effect difference, there is at following 2 points：
1. coking chemical waste water contains phenols, cyanogen class material to the toxic inhibitory action of microorganism, cause biochemical system removal efficiency not It is high；
2. containing refractory organic in coking chemical waste water, depend merely on biochemical treatment and be difficult to reach index request.
Coking distilled ammonia wastewater is only with biochemical treatment in summary, it is difficult to reaches discharge or reuse standard, it is necessary to its depth Degree processing.Have at 2 points to the technique starting point of its advanced treating：First, strengthening pretreatment, Phenol for Waste Water cyanogen class material is reduced to life The inhibitory action of change system, and the processing load of biochemical system is reduced, play the maximum efficiency of biochemical system；Second, biochemistry is gone out Water carries out advanced treating using advanced oxidation processes, reduces the content of refractory organic, reaches discharge or reuse requirement.
The content of the invention
The present invention provides a kind of method of coking distilled ammonia wastewater advanced treating, and the invention utilizes pretreatment+biochemical treatment+height Level oxidation depth processing group technology coking distilled ammonia wastewater is handled, make the coking distilled ammonia wastewater qualified discharge after processing or Reuse, the technical scheme of use are：A kind of coking distilled ammonia wastewater deep treatment method, it is characterised in that：The processing method bag Include following processing step：
A. the coal tar demulsification of emulsification state, the Production Wastewater By Combined Acidification And Demulsification step of formation suspension, acidifying solution pH value are controlled in 1.5-3.5, The demulsification time is 1-3 hours；
B. promote coal tar to separate out and aoxidize the phenols for being dissolved in water and the ozone pre-oxidation step of cyanogen class material, ozone dosage are 50-200mg/L, preoxidation time are 20-60 minutes；
C. the air supporting step separated the coal tar after demulsification and water, hydraulic detention time is 10-60 minutes；
D. the secondary filter step of two dephenolize oil removings；
E. to the light electrolysis step of organic matter open loop chain rupture while removal partial organic substances, it is 2-3 to enter water management water inlet pH value, It is 3-4 to go out water management pH value, and the light electrolysis time is 15-120 minutes；
F. it is the Fenton oxygen that catalyst carries out quadric catalysis oxidation to organic matter using ferrous ion caused by weak electrolysis mechanism Change step, it is 0.5 ‰ -10 ‰ to add 30% dioxygen water, and oxidization time is 15-60 minutes, and Fenton goes out water ph value and adds alkali to pull back to PH value 8-9；
G. anoxic/the aerobic biochemical being removed using anoxic and aerobic microbiological to the organic matter in waste water, ammonia nitrogen and total nitrogen Step, wherein anoxic pond sludge concentration are 4000-6000mg/L, and dissolved oxygen is<0.5mg/L, pH value 6.0-8.0；Aerobic Pond Sludge concentration is 3000-5000mg/L, dissolved oxygen 2.0-6.0mg/L, pH 6.0-9.0；
H. the catalytic and oxidative electrolysis technology step of advanced treating is carried out to organic matter and ammonia nitrogen.
The technical characteristic of the present invention also has：Micro-electrolysis stuffing is by iron powder and carbon dust and catalytic component, viscous in the step e Mixture, pore creating material mixed-forming according to a certain percentage, are formed through anoxybiotic high-temperature roasting.
The technical characteristic of the present invention also has：Catalytic and oxidative electrolysis technology reactor is square structure in the h steps, in reactor Parallel arranged at least one set positive and negative pole, positive and negative pole are alternately arranged, and anode is ti-based coating electrode, coating material PbO2, IrO2,TaO2In one or more, negative electricity extremely stainless steel electrode or graphite electrode.
The technical characteristic of the present invention also has：Current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm.
The beneficial effects of the present invention are：1）Detar technique make it that pretreating process is more perfect, reduces light electrolysis Caused by filler plugging rate, and ozone pre-oxidation also improves the removal effect of light electrolysis and Fenton in pre-processing, stability and Treatment effeciency is good；
2）Coking distilled ammonia wastewater is carried out using Production Wastewater By Combined Acidification And Demulsification+ozone pre-oxidation+air supporting+secondary filter+light electrolysis+Fenton technology Pretreatment, first, coal tar can be removed farthest, ensure that the stability of subsequent technique；Second, improve waste water can Biochemical, subsequent biochemical technique is set to play maximal efficiency；Third, oxidation removal phenols, cyanogen class etc. are to the toxic effect of microorganism Organic matter, ensure that biochemical process stability and processing load；
3）Respectively coking distilled ammonia wastewater is pre-processed to improve biodegradability, processing cost economy is realized in biochemical treatment Property, advanced treating ensure processing depth, both ensure that treatment effect, and reduced processing cost again；
4）Processing cost is low.Whole set process has played the maximal efficiency of biochemical process, and biochemical by biochemical pre-treatment raising Property and biochemical rear oxidation remove bio-refractory organic matter, reduce processing cost on the premise for the treatment of effect is ensured.
5）Treatment effect can reach《Integrated wastewater discharge standard》To COD, ammonia nitrogen, total nitrogen index in GB8978-1996 The requirement of concentration of emission limit value.
Brief description of the drawings
Accompanying drawing 1 is present invention process flow chart.
Embodiment
A kind of coking distilled ammonia wastewater deep treatment method, technological process is as shown in figure 1, methods described is come by the following means Coking distilled ammonia wastewater is handled：Pending waste water adds acid for adjusting pH Production Wastewater By Combined Acidification And Demulsification pond after 1.5-3.5 to be demulsified first Oil removing, 1-3 hours Production Wastewater By Combined Acidification And Demulsification time；Production Wastewater By Combined Acidification And Demulsification water outlet enters ozone pre-oxidation pond after adding 50-200mg/L ozone, in advance Oxidization time is 20-60 minutes；Ozone pre-oxidation water outlet enters air supporting and carries out water-oil separating, and air supporting hydraulic detention time is 10- 60 minutes；Air supporting water outlet enters the secondary filter unit that filtering accuracy is 0.05um and carries out secondary oil removing, secondary filter backwash water It is back to air flotation cell；Secondary filter water outlet is aoxidized into light electrolysis, is removed partial organic substances and is improved biodegradability, micro- The electrolytic oxidation time is 15-120 minutes；Light electrolysis water outlet enters Fenton oxidation progress 15- after adding 0.5 ‰ -10 ‰ hydrogen peroxide Aoxidize within 60 minutes, further reduce content of organics；Fenton water outlet precipitates after adding alkali regulation PH7.0-9.0 into sedimentation basin 1 1.0-4.0 hour carries out mud-water separation；The water outlet of sedimentation basin 1 enters anoxic biological tank, keeps sludge 4000- in anoxic biological tank 6000mg/L, dissolved oxygen control are 6-9 in below 0.5mg/L, pH value control, and muddy water hybrid mode uses mechanical agitation under liquid, Hydraulic detention time is 20-60 hours, and the nitrate in water is converted into nitrogen by denitrifying bacterium under anoxic conditions and overflowed, anoxic Biological tank water outlet enters aerobe pond, and it is 3000-5000mg/L to keep suspended sludge concentration in aerobic biochemical pool, and dissolved oxygen exists 2.0-6.0mg/L, pH value 6-9, hydraulic detention time are 20-60 hours, and partial organic substances and ammonia nitrogen are by aerobic micro- life in water Thing is decomposed into CO2、H2O、NO3 2-, aerobe pond water part is back to anoxic biological tank 1 by reflux ratio 100%-400% and removed NO3 2-, the water outlet of aerobe pond, which enters in sedimentation basin 2, carries out mud-water separation, and base sludge is back to anoxic biological tank, supernatant Deep oxidation is carried out into catalytic and oxidative electrolysis technology unit, current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm； Waste water aoxidizes qualified discharge after 30-120 minutes in catalytic and oxidative electrolysis technology unit.
Below according to described above, typical industrial wastewater is selected to carry out specific implementation explanation for process object.
Embodiment 1
Certain coke-oven plant's distilled ammonia wastewater：COD is 2600mg/L, ammonia nitrogen 1100mg/L, total nitrogen 1500mg/L.
Handled using processing method provided by the invention：Pending waste water adds acid for adjusting pH to be acidified after 3.5 first Be demulsified pond progress breaking milk and removing oil, 1 hour Production Wastewater By Combined Acidification And Demulsification time；Production Wastewater By Combined Acidification And Demulsification water outlet enters the pre- oxygen of ozone after adding 50mg/L ozone Change pond, preoxidation time is 20 minutes；Ozone pre-oxidation water outlet enters air supporting and carries out water-oil separating, and air supporting hydraulic detention time is 10 minutes；Air supporting water outlet enters the secondary filter unit that filtering accuracy is 0.05um and carries out secondary oil removing, secondary filter backwash water It is back to air flotation cell；Secondary filter water outlet is aoxidized into light electrolysis, is removed partial organic substances and is improved biodegradability, micro- The electrolytic oxidation time is 15 minutes；Light electrolysis water outlet enters Fenton oxidation progress oxidation in 15 minutes after adding 0.5 ‰ hydrogen peroxide, enters One step reduces content of organics；Fenton water outlet enters 1.0 hours progress mud-water separations of the precipitation of sedimentation basin 1 after adding alkali regulation pH7.0； The water outlet of sedimentation basin 1 enters anoxic biological tank, keeps sludge 4000mg/L in anoxic biological tank, dissolved oxygen control 0.5mg/L with Under, pH value control is 6.0, and muddy water hybrid mode uses mechanical agitation under liquid, and hydraulic detention time is 20-60 hours, in water Nitrate is converted into nitrogen by denitrifying bacterium under anoxic conditions and overflowed, and the water outlet of anoxic biological tank enters aerobe pond, keeps Suspended sludge concentration is 3000-5000mg/L in aerobe pond, and dissolved oxygen is in 6.0mg/L, pH value 6, hydraulic detention time For 20 hours, partial organic substances and ammonia nitrogen were decomposed into CO by aerobic microbiological in water2、H2O、NO3 2-, aerobe pond water part Anoxic biological tank 1, which is back to, by reflux ratio 100% removes NO3 2-, the water outlet of aerobe pond, which enters, carries out muddy water point in sedimentation basin 2 Anoxic biological tank is back to from, base sludge, and supernatant enters catalytic and oxidative electrolysis technology unit and carries out deep oxidation, electric current between pole plate Density is 5.0mA/cm, and pole plate spacing is 5cm；Qualified discharge after waste water aoxidizes 30 minutes in catalytic and oxidative electrolysis technology unit.
Water outlet COD is 35mg/L, ammonia-nitrogen content 0.5mg/L, total nitrogen content 12mg/L.
Embodiment 2
Distilled ammonia wastewater caused by certain steel joint factory's coking workshop：COD is 6500mg/L, ammonia nitrogen 2200mg/L, and total nitrogen is 2500mg/L。
Handled using processing method provided by the invention：Pending waste water adds acid for adjusting pH to be acidified after 1.5 first Be demulsified pond progress breaking milk and removing oil, 3 hours Production Wastewater By Combined Acidification And Demulsification time；It is pre- to enter ozone after Production Wastewater By Combined Acidification And Demulsification water outlet addition 200mg/L ozone Oxidation pond, preoxidation time are 60 minutes；Ozone pre-oxidation water outlet enters air supporting and carries out water-oil separating, air supporting hydraulic detention time For 60 minutes；Air supporting water outlet enters the secondary filter unit that filtering accuracy is 0.05um and carries out secondary oil removing, secondary filter backwash Water is back to air flotation cell；Secondary filter water outlet is aoxidized into light electrolysis, is removed partial organic substances and is improved biodegradability, Light electrolysis oxidization time is 120 minutes；Light electrolysis water outlet enters Fenton oxidation progress oxidation in 60 minutes after adding 10 ‰ hydrogen peroxide, Further reduce content of organics；Fenton water outlet enters 4.0 hours progress muddy water point of the precipitation of sedimentation basin 1 after adding alkali regulation pH9.0 From；The water outlet of sedimentation basin 1 enters anoxic biological tank, keeps sludge 6000mg/L in anoxic biological tank, and dissolved oxygen is controlled in 0.5mg/L Hereinafter, pH value control is 9, and muddy water hybrid mode uses mechanical agitation under liquid, and hydraulic detention time is 60 hours, the nitric acid in water Salt is converted into nitrogen by denitrifying bacterium under anoxic conditions and overflowed, and the water outlet of anoxic biological tank enters aerobe pond, keeps aerobic Suspended sludge concentration is 5000mg/L in biological tank, and dissolved oxygen is 60 small in 6.0mg/L, pH value 9.0, hydraulic detention time When, partial organic substances and ammonia nitrogen are decomposed into CO by aerobic microbiological in water2、H2O、NO3 2-, aerobe pond water part is by backflow Anoxic biological tank 1 is back to than 400% and removes NO3 2-, the water outlet of aerobe pond, which enters in sedimentation basin 2, carries out mud-water separation, bottom Sludge reflux is to anoxic biological tank, and supernatant enters catalytic and oxidative electrolysis technology unit and carries out deep oxidation, and current density is between pole plate 20mA/cm, pole plate spacing are 1cm；Qualified discharge after waste water aoxidizes 120 minutes in catalytic and oxidative electrolysis technology unit.
Water outlet COD is 48mg/L, ammonia-nitrogen content 0.2mg/L, total nitrogen content 10mg/L, and processing cost is 17 yuan/m3。
Embodiment 3
Coking distilled ammonia wastewater caused by certain coal tar joint factory：COD is 4000mg/L, ammonia nitrogen 1300mg/L, total nitrogen 1740mg/L.
Handled using processing method provided by the invention：Pending waste water adds acid for adjusting pH to be acidified after 2.5 first Be demulsified pond progress breaking milk and removing oil, Production Wastewater By Combined Acidification And Demulsification time 2 h；It is pre- to enter ozone after Production Wastewater By Combined Acidification And Demulsification water outlet addition 100mg/L ozone Oxidation pond, preoxidation time are 30 minutes；Ozone pre-oxidation water outlet enters air supporting and carries out water-oil separating, air supporting hydraulic detention time For 30 minutes；Air supporting water outlet enters the secondary filter unit that filtering accuracy is 0.05um and carries out secondary oil removing, secondary filter backwash Water is back to air flotation cell；Secondary filter water outlet is aoxidized into light electrolysis, is removed partial organic substances and is improved biodegradability, Light electrolysis oxidization time is 60 minutes；Light electrolysis water outlet enters Fenton oxidation progress oxidation in 30 minutes after adding 5 ‰ hydrogen peroxide, enters One step reduces content of organics；Fenton water outlet enters 2.0 hours progress mud-water separations of the precipitation of sedimentation basin 1 after adding alkali regulation pH8.0； The water outlet of sedimentation basin 1 enters anoxic biological tank, keeps sludge 5000mg/L in anoxic biological tank, dissolved oxygen control 0.5mg/L with Under, pH value control is 7.0, and muddy water hybrid mode uses mechanical agitation under liquid, and hydraulic detention time is 40 hours, the nitric acid in water Salt is converted into nitrogen by denitrifying bacterium under anoxic conditions and overflowed, and the water outlet of anoxic biological tank enters aerobe pond, keeps aerobic Suspended sludge concentration is 4000mg/L in biological tank, and dissolved oxygen is 40 small in 4.0mg/L, pH value 7.0, hydraulic detention time When, partial organic substances and ammonia nitrogen are decomposed into CO by aerobic microbiological in water2、H2O、NO3 2-, aerobe pond water part is by backflow Anoxic biological tank 1 is back to than 200% and removes NO3 2-, the water outlet of aerobe pond, which enters in sedimentation basin 2, carries out mud-water separation, bottom Sludge reflux is to anoxic biological tank, and supernatant enters catalytic and oxidative electrolysis technology unit and carries out deep oxidation, and current density is between pole plate 10mA/cm, pole plate spacing are 3cm；Qualified discharge after waste water aoxidizes 60 minutes in catalytic and oxidative electrolysis technology unit.
Water outlet COD is 38mg/L, ammonia-nitrogen content 0.8mg/L, total nitrogen content 8mg/L, and processing cost is 15 yuan/m3。

Claims (4)

  1. A kind of 1. coking distilled ammonia wastewater deep treatment method, it is characterised in that：It the treating method comprises following processing step：
    A. the coal tar demulsification of emulsification state, the Production Wastewater By Combined Acidification And Demulsification step of formation suspension, acidifying solution pH value are controlled in 1.5-3.5, The demulsification time is 1-3 hours；
    B. promote coal tar to separate out and aoxidize the phenols for being dissolved in water and the ozone pre-oxidation step of cyanogen class material, ozone dosage are 50-200mg/L, preoxidation time are 20-60 minutes；
    C. the air supporting step separated the coal tar after demulsification and water, hydraulic detention time is 10-60 minutes；
    D. the secondary filter step of two dephenolize oil removings；
    E. to the light electrolysis step of organic matter open loop chain rupture while removal partial organic substances, it is 2-3 to enter water management water inlet pH value, It is 3-4 to go out water management pH value, and the light electrolysis time is 15-120 minutes；
    F. it is the Fenton oxygen that catalyst carries out quadric catalysis oxidation to organic matter using ferrous ion caused by weak electrolysis mechanism Change step, it is 0.5 ‰ -10 ‰ to add 30% dioxygen water, and oxidization time is 15-60 minutes, and Fenton goes out water ph value and adds alkali to pull back to PH value 8-9；
    G. anoxic/the aerobic biochemical being removed using anoxic and aerobic microbiological to the organic matter in waste water, ammonia nitrogen and total nitrogen Step, wherein anoxic pond sludge concentration are 4000-6000mg/L, and dissolved oxygen is<0.5mg/L, pH value 6.0-8.0；Aerobic Pond Sludge concentration is 3000-5000mg/L, dissolved oxygen 2.0-6.0mg/L, pH 6.0-9.0；
    H. the catalytic and oxidative electrolysis technology step of advanced treating is carried out to organic matter and ammonia nitrogen.
  2. 2. according to the deep treatment method described in claim 1, it is characterised in that：Micro-electrolysis stuffing is by iron powder in the step e With carbon dust and catalytic component, adhesive, pore creating material mixed-forming according to a certain percentage, formed through anoxybiotic high-temperature roasting.
  3. 3. according to the deep treatment method described in claim 1, it is characterised in that：Catalytic and oxidative electrolysis technology reacts in the h steps Device is square structure, and parallel arranged at least one set positive and negative pole in reactor, positive and negative pole is alternately arranged, and anode is ti-based coating electricity Pole, coating material PbO2,IrO2,TaO2In one or more, negative electricity extremely stainless steel electrode or graphite electrode.
  4. 4. according to the deep treatment method described in claim 3, it is characterised in that：Current density is 5.0-20mA/cm between pole plate, Pole plate spacing is 1-5cm.
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CN111807590A (en) * 2019-04-12 2020-10-23 江苏南大环保科技有限公司 Resource treatment method for exempting dangerous waste of high ammonia nitrogen wastewater in coal chemical industry
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CN114477629A (en) * 2022-01-21 2022-05-13 南京高科环境科技有限公司 Treatment system and treatment method for viscose flushing wastewater
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CN108892309A (en) * 2018-06-25 2018-11-27 河钢股份有限公司 A kind of high-efficient treatment method being suitble to coking wastewater difficult to degrade
CN109399862A (en) * 2018-11-07 2019-03-01 四川众兴汽车零部件有限公司 A kind of industrial wastewater treatment system and its processing method
CN109231715A (en) * 2018-11-09 2019-01-18 鞍钢股份有限公司 Method for treating chemical ammonia distillation wastewater
CN111807590A (en) * 2019-04-12 2020-10-23 江苏南大环保科技有限公司 Resource treatment method for exempting dangerous waste of high ammonia nitrogen wastewater in coal chemical industry
CN111807590B (en) * 2019-04-12 2022-03-08 江苏南大环保科技有限公司 Resource treatment method for exempting dangerous waste of high ammonia nitrogen wastewater in coal chemical industry
CN110395856A (en) * 2019-09-04 2019-11-01 河北逾净环保科技有限公司 A kind of processing method of electrophoretic-coating wastewater
CN110902956A (en) * 2019-12-06 2020-03-24 广东石油化工学院 Coking wastewater treatment method
CN114906973A (en) * 2021-02-09 2022-08-16 高峰 Coking sewage advanced treatment zero-discharge process
CN113912237A (en) * 2021-10-29 2022-01-11 山东亚泰国宇环保科技有限公司 Heavy-pollution semi-coke wastewater treatment process
CN114315011A (en) * 2021-12-01 2022-04-12 江苏同瑞环保有限公司 Coking wastewater treatment system and coking wastewater treatment method
CN114177934A (en) * 2021-12-28 2022-03-15 华夏碧水环保科技有限公司 Treatment method of coking ammonia distillation wastewater and heterogeneous Fenton catalyst used in treatment method
CN114177934B (en) * 2021-12-28 2024-01-16 华夏碧水环保科技股份有限公司 Treatment method of coking ammonia distillation wastewater and heterogeneous Fenton catalyst used in treatment method
CN114477629A (en) * 2022-01-21 2022-05-13 南京高科环境科技有限公司 Treatment system and treatment method for viscose flushing wastewater
CN114477629B (en) * 2022-01-21 2023-05-02 南京高科环境科技有限公司 System and method for treating sticky flushing wastewater
CN116282698A (en) * 2023-03-06 2023-06-23 武汉天源环保股份有限公司 Sewage treatment system and method

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