CN108395051A - A kind of coking wastewater short-range nitration method of stability and high efficiency - Google Patents

A kind of coking wastewater short-range nitration method of stability and high efficiency Download PDF

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Publication number
CN108395051A
CN108395051A CN201710068953.5A CN201710068953A CN108395051A CN 108395051 A CN108395051 A CN 108395051A CN 201710068953 A CN201710068953 A CN 201710068953A CN 108395051 A CN108395051 A CN 108395051A
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China
Prior art keywords
coking wastewater
wastewater
stability
high efficiency
coking
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CN201710068953.5A
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Inventor
陈鹏
胡绍伟
李林
孙静
龙海萍
张彦
王飞
刘芳
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Angang Steel Co Ltd
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Angang Steel 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
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • 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
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F3/02Aerobic processes
    • C02F3/12Activated sludge processes

Abstract

The present invention discloses a kind of coking wastewater short-range nitration method of stability and high efficiency, rationally the temperature condition needed for reaction system is maintained using the residual heat resources of chemical industry distilled ammonia wastewater, realize steel mill's residual heat resources effective recycling, save the thermal energy consumption to maintain short distance nitration reaction required temperature to heat under normal condition, the short distance nitration of stability and high efficiency is finally realized in MBR, it not only greatly reduces the operating cost of wastewater treatment, but also lays a good foundation for subsequent denitrification denitrogenation and the final qualified discharge of coking wastewater.

Description

A kind of coking wastewater short-range nitration method of stability and high efficiency
Technical field
The invention belongs to industrial waste water treatment more particularly to a kind of coking wastewater short distance nitrations of stability and high efficiency Method.
Background technology
Coking wastewater is the waste water that High T-emperature Carbonization is formed in the process and in gas purification, chemical products subtractive process, Complicated component, pollutant concentration is high, coloration is high, toxicity is big, and property is highly stable, and biodegradability is poor, is discharged ammonia nitrogen and COD occupies height Under not, recently as the increasingly stringent of environmental protection standard, the total nitrogen of sewage discharge is also limited, coking wastewater is reached More stringent requirements are proposed for mark discharge.
In recent years, by constantly studying and putting into practice, domestic and foreign scholars have found many technologies for administering coking wastewater, main There are biological treatment, method of chemical treatment, physicochemical treatment method and achieves certain treatment effect.The current coking in China is useless Water treatment technology is applied to mainly have anaerobic-aerobic process (A/O), the aerobic (A/O of anaerobic-aerobic-in engineering2), anaerobism-lack Oxygen-aerobic method (A2/ O), the anaerobism-level-one aerobic-anaerobic-aerobic (A of two level2/O2) etc., coking wastewater index is substantially steady after processing It is scheduled on the secondary discharge standard of GB8978-1996, especially COD and NH3The two indexs of-N are difficult to reach emission request simultaneously.
Traditional bio-denitrification technology think the ammoniacal nitrogen in water to be completely removed just have to by completely nitrify with Denitrification process, the i.e. terminal using nitrate as nitrification and denitrifying starting point.Many scholars are anti-to short distance nitration in recent years Nitrification denitrogenation technology has carried out numerous studies, and short-cut nitrification and denitrification technology in the nitrification stage due to reducing NO2 --NO3 -It is anti- Answer process, the dosage of organic carbon source that can generally reduce 40%, oxygen demand can at least reduce by 25%, not only shorten the reaction time, Reduce reactor volume, reduce investment and operating cost, and reduce energy consumption, improves nitric efficiency and traditional Sewage water denitrification technology is compared, and is had wide development space, has been caused the extensive concern of domestic and international researcher.
It is new by looking into, some relevant patents and article are retrieved, such as " energy-saving process for treating high ammonia nitrogen waste water " (CN101195513), this method first makes waste water convert triumphant formula nitrogen to ammonia nitrogen by pretreatment, subsequently into short distance nitration pond In, Ammonia Nitrification was controlled in the nitrite nitrogen stage, then micro-electrolysis reactor is utilized to substitute anaerobic denitrifying or ammoxidation Technique carries out denitrogenation processing, then makees subsequent processing with bioanalysis or Fenton oxidation method, materialization oxidizing process, and nitrogen removal rate reaches 60%-75%.This method is mainly used for high NH_3-N treating, still undesirable to hardly degraded organic substance processing." the processing of coking wastewater Coking wastewater is passed through oil separator, regulating reservoir, iron carbon-Fenton oxidation pond, up-flow by method " (CN 101781067A), this patent Formula anaerobic mud bed reactor, hydrolysis multi-function pool, anoxic pond, complex enzyme/activated sludge pond and secondary settling tank, then discharge water outlet.This Processing structures needed for kind method are more, and complex process takes up a large area, and operating cost is also higher.A kind of " Treatment of Coking Effluent Process " (CN200810234318.0), this method are made of physicochemical treatment unit and biochemical treatment unit, wherein at materialization Reason unit is made of micro-electrolysis reactor, sedimentation basin, and micro-electrolysis reactor is to fill out with waste iron filing, copper scrap bits and lightweight bulk material Material.Biochemical treatment unit is made of inside circulation triphase fluidized bed reactor, is realized using immobilized active sludge bead while de- Nitrogen removes carbon.Although water outlet volatile phenol, ammonia nitrogen, coloration can reach integrated wastewater discharge standard primary standard, COD treatment effects It is unsatisfactory, it is only capable of reaching integrated wastewater discharge standard secondary standard." one kind obtaining stable nitrite by sewage denitrification The method of accumulation " (CN101602545A), this method are adjusted the carbon-nitrogen ratio of sewage with methanol or other additional carbons, utilize pH value Variation characteristic instruction activated sludge process denitrification process, the nitrate in sewage is changed into nitrite by final realize, To obtain stable nitrite accumulation.But this method needs additional carbon, increases the processing cost of sewage, and obtain Nitrite accumulation amount is 25% or so of the initial nitrate total amount of reaction, and accumulation is not very high.
In conclusion coking wastewater realizes final qualified discharge, the Nitrogen removal effect for obtaining stability and high efficiency early period is extremely closed It is important, it is therefore necessary to develop a kind of high treating effect, technological process is simple, and equipment operation and investment cost all compare conjunction It is important will finally to realize coking wastewater the sustainable development of qualified discharge and coal chemical enterprise has for the bio-denitrification technology of reason Realistic meaning.
Invention content
In view of the foregoing drawbacks, the technical problems to be solved by the invention provide a kind of coking wastewater short distance nitre of stability and high efficiency Change method, by the short distance for reasonably making biochemical section acquisition stability and high efficiency using the useless residual heat resources of steel mill and control reaction condition Nitrification effect reduces cost for wastewater treatment, and base is established for the denitrification denitrogenation and final qualified discharge of follow-up coking wastewater Plinth..
To achieve the goals above, the technical solution adopted by the present invention is such:
A kind of coking wastewater short-range nitration method of stability and high efficiency, it is characterised in that:The water of coking wastewater to be dealt with Matter is COD:2500-3500mg/L, NH4 +-N:100-300mg/L, pH:7-8, the coking wastewater through gravity oil-removing is in heat exchanger Heat exchange, 15-25 DEG C of coking wastewater temperature, 90-95 DEG C of distilled ammonia wastewater, the coking wastewater inflow after heating are carried out with distilled ammonia wastewater In aerobic membrane bioreactor, 35-45 DEG C of control coking wastewater temperature, the distilled ammonia wastewater of cooling comes back to coking wastewater system In;The seed sludge of MBR is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4000-5000mg/L of sludge seeding is opened Dynamic stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist;Then control reactor In dissolved oxygen concentration be 0.5-0.9mg/L, pH 8-9, the hydraulic detention time of reactor is 18-22h, NH of intaking4 +- N's Volumetric loading is 0.24-0.32gNH4 +-N/(L·d);With the increase of running time, the NO in water outlet3 -- N concentration gradually subtracts It is few, NO2 -The concentration of-N gradually increases, and runs 8-12 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio can reach 90% or more, the short distance nitration effect of stability and high efficiency is obtained, base has been established for subsequent denitrification denitrogenation and Anammox Plinth.
The beneficial effects of the invention are as follows:Rationally maintained needed for reaction system using the residual heat resources of chemical industry distilled ammonia wastewater Temperature condition realizes steel mill's residual heat resources effective recycling, saves under normal condition as needed for maintenance short distance nitration reaction Temperature and the thermal energy consumption heated, the short distance nitration of stability and high efficiency is finally realized in MBR, is not only greatly reduced at waste water The operating cost of reason, and lay a good foundation for subsequent denitrification denitrogenation and the final qualified discharge of coking wastewater.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific implementation mode
With reference to embodiment, the present invention is described in detail.
Embodiment 1:
Coking wastewater (temperature is 15 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 90 DEG C) Heat exchange, it is 35 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4000mg/L of sludge seeding starts Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor Dissolved oxygen concentration be 0.5mg/L, pH 8, control reactor hydraulic detention time be 18h, intake NH4 +The volumetric loading of-N For 0.24gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -The concentration of-N It gradually increases, runs 8 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 91%, obtains stability and high efficiency NO2 -The accumulation of-N creates good flow condition for subsequent denitrification denitrogenation and being smoothed out for Anammox reaction.
Embodiment 2:
Coking wastewater (temperature is 20 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 93 DEG C) Heat exchange, it is 40 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4500mg/L of sludge seeding starts Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor Dissolved oxygen concentration be 0.7mg/L, pH 8.5, control reactor hydraulic detention time be 20h, intake NH4 +The volume of-N is negative Lotus is 0.28gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -- N's is dense Degree gradually increases, and runs 10 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 93%, obtains stability and high efficiency NO2 -The accumulation of-N creates good into water bar for being smoothed out of reacting of subsequent denitrification denitrogenation and Anammox Part.
Embodiment 3:
Coking wastewater (temperature is 25 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 95 DEG C) Heat exchange, it is 45 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 5000mg/L of sludge seeding starts Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor Dissolved oxygen concentration be 0.9mg/L, pH 9.0, control reactor hydraulic detention time be 22h, intake NH4 +The volume of-N is negative Lotus is 0.32gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -- N's is dense Degree gradually increases, and runs 12 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 94%, obtains stability and high efficiency NO2 -The accumulation of-N creates good into water bar for being smoothed out of reacting of subsequent denitrification denitrogenation and Anammox Part.

Claims (1)

1. a kind of coking wastewater short-range nitration method of stability and high efficiency, it is characterised in that:The water quality of coking wastewater to be dealt with For COD:2500-3500mg/L, NH4 +-N:100-300mg/L, pH:7-8, the coking wastewater through gravity oil-removing in heat exchanger with Distilled ammonia wastewater progress heat exchange, 15-25 DEG C of coking wastewater temperature, 90-95 DEG C of distilled ammonia wastewater, the coking wastewater after heating flow into In aerobic membrane bioreactor, 35-45 DEG C of control coking wastewater temperature, the distilled ammonia wastewater of cooling comes back to coking wastewater system In;The seed sludge of MBR is derived from the nitrifying sludge of chemical plant aerobic tank, initial a concentration of 4000-5000mg/L of sludge seeding;With It is 0.5-0.9mg/L to control the dissolved oxygen concentration in reactor afterwards, and the hydraulic detention time of pH 8-9, reactor are 18-22h, Water inlet NH4 +The volumetric loading of-N is 0.24-0.32gNH4 +-N/(L·d);Operation 8-12 days, membrane bioreactor water outlet NO2 --N/NOxN ratio reaches 90% or more.
CN201710068953.5A 2017-02-08 2017-02-08 A kind of coking wastewater short-range nitration method of stability and high efficiency Pending CN108395051A (en)

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CN105481099A (en) * 2014-09-19 2016-04-13 鞍钢股份有限公司 Treatment method of oil-removed coking wastewater
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